DMD based UV absorption detector for liquid chromatography

ABSTRACT

A detector for use in liquid chromatography is provided. The detector includes a light delivery system comprising a light source that emits one or more spectral lines of light of a light spectrum. The detector has an entrance slit configured to receive the one or more spectral lines of light and a wavelength selection module comprising a digital micro-mirror device. The digital micro-mirror device is configured to redirect the one or more spectral lines of light to a flow cell. The flow cell is optically connected to the wavelength selection module.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/772,109 filed on Apr. 30, 2018, which is a U.S. National StageApplication of International Patent Application No. PCT/US16/60323 filedon Nov. 3, 2016, which claims priority to U.S. Provisional PatentApplication No. 62/250,092 filed Nov. 3, 2015, all of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

In a liquid chromatography ultraviolet detector, resolution can directlyimpact the capabilities of the instrument to uniquely identifysubstances. Resolution is the measure, in nanometers, of how far apartin wavelength two light signals are so that the detector can accuratelybe distinguished one from the other. Many variables can impactresolution, however. For example, two factors that set the maximumtheoretical resolution are slit width and linear dispersion of thediffraction grating. Thevenon, J. M. L. and A., A Tutorial onSpectroscopy, 2003.

Other factors that can impact the ultraviolet detector include opticalbandwidth, wavelength range and dynamic capability. The opticalbandwidth of a detector is the breadth of the minimum spectra that amachine is capable of detecting. It can be equal to, or more often,greater than the resolution of the detector. For example, if aninstrument has a resolution of 1 nm and an optical bandwidth of 5 nm,the detector can detect absorption between 250 nm and 255 nm or between251 nm and 256 nm. Wavelength range is the portion of theelectromagnetic spectrum in which a detector can operate and is seteither by the spectral distribution of the light source or the design ofthe optical system. Methods for absorption spectroscopy are oftendesigned around a specific wavelength or set of wavelengths. Therefore,a range of wavelengths over which a detector can operate oftendetermines its useful application.

Likewise, the noise arising from the quantized nature of light, calledthe shot noise, often dominates the signal to noise ratio (“SNR”) in UVdetectors. Yariv, A., Introduction to Optical Electronics Holt, Rinehart& Winston Series in Electrical Engineering, Electronics, and Systems,2nd ed. Holt, Rinehart and Winston, 1976. Often liquid chromatography isused as a method to determine not what a sample is composed of, butrather how much of a given substance is present in the sample. Yet,nearly every component of the detector and its environment has thepotential to add some amount of noise to the signal. The addition of areference can reduce or eliminate many forms of noise.

Furthermore, dynamic capabilities of a detector, or the set of featureswhich can be used while samples are running, such as reference-basednoise canceling, baseline adjustments, on-the-fly self-calibration,timesharing among multiple wavelengths, and actively modulating thesource or entrance slit, often are lacking in the device. Dynamicfeatures add flexibility and robustness to a detector, and provide adevice for backwards and forwards compatibility.

A need exists for the liquid chromatography detector that is efficient,compact having low heat generation and dynamic in nature, having bothbackwards and forwards compatibility.

SUMMARY OF THE INVENTION

In one example, a detector for liquid chromatography includes a lightdelivery system and a wavelength selection module. The light deliverysystem includes a light source that emits light having a plurality ofwavelengths. The wavelength selection module is optically coupled to thelight delivery system and includes a spectrally dispersive opticalelement and a digital micro-mirror device. The spectrally dispersiveoptical element receives the light from the light delivery system andprovides diffracted light having a linear dispersion of the wavelengths.The digital micro-mirror device is configured to receive the diffractedlight and to selectively reflect one or more of the wavelengths into anoutput beam.

The detector may further include a flow cell disposed along an opticalpath between the light delivery system and the wavelength selectionmodule. The detector may further include a flow cell disposed to receivethe output beam of the wavelength selection module. The detector mayfurther include a focusing element that optically couples the lightdelivery system to the wavelength selection module.

The wavelength selection module may include an optical attenuator. Thespectrally dispersive optical element may include a focusing element anda grating. The spectrally dispersive element may be a concave grating.The digital micro-mirror device may be configurable as a variable slithaving a dynamically defined width and a height.

The linear dispersion of the wavelengths may be an angular dispersion ofthe wavelengths in the diffracted light provided by the spectrallydispersive optical element. The output beam of the wavelength selectionmodule may include one or more wavelengths selected to match one or morespectral absorption features of an analyte of interest. The plurality ofwavelengths may include a plurality of ultraviolet wavelengths.

The detector may further include an optical output subsystem in opticalcommunication with the digital micro-mirror device to receive the outputbeam wherein the optical output subsystem is configured to shape anddirect the output beam. The optical output subsystem may be configuredto focus the selectively reflected wavelengths of the diffracted lightinto a single image at an output image surface and may include at leastone focusing element and a spectrally dispersive optical element. Theoptical output subsystem may include a focusing element that focuses theselectively reflected wavelengths of the diffracted light into spatiallyresolved images at an output image surface. A light detector may bedisposed at the output image surface to receive one of the spatiallyresolved images. The light detector may include one or more photodiodes.

The wavelength selection module may further include a second digitalmicro-mirror device disposed between the light delivery system and thespectrally dispersive optical element. The second digital micro-mirrordevice has a plurality of micro-mirrors configurable to define avariable entrance slit having a width and a height determined by anorientation of a plurality of the micro-mirrors.

The wavelength selection module may further include a second digitalmicro-mirror device positioned to receive the output beam from the firstdigital micro-mirror device. The second digital micro-mirror device hasa plurality of micro-mirrors configurable to define a variable exit slithaving a width and a height determined by an orientation of a pluralityof the micro-mirrors.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents a basic liquid chromatography process and set up, andcomponents.

FIG. 2A provides a general diagram of an optical-based detector forliquid chromatography in which the flow cell is after the wavelengthselection module.

FIG. 2B provides a diagram of an optical-based detector for liquidchromatography where the flow cell precedes the wavelength selectionmodule.

FIG. 2C provides a layout of the detector described herein.

FIG. 3A provides a general diagram of a prior art optical-based detectorfor liquid chromatography in which the flow cell is after the wavelengthselection module.

FIG. 3B provides a diagram of a prior art optical-based detector forliquid chromatography where the flow cell precedes the wavelengthselection module.

FIG. 4 illustrates an embodiment of the present detector in which adigital micro-mirror device (“DMD”) is positioned at or near a focalplane of a spectrograph.

FIG. 5A illustrates methods of focusing a light beam from the DMDthrough an optical output system (a component of the detector) intodistinct images.

FIG. 5B illustrates the methods of FIG. 5A with optical output systemconfigured to achieve a common focus for all wavelengths.

FIG. 6 and FIG. 7 demonstrate Snell's law for Total Internal Reflection.

FIG. 8 shows optical coupling for elements with mismatched numericalapertures.

FIGS. 9A, 9B and 9C show Fraunhofer Diffraction Patterns for a singleentrance slit (FIG. 9A), a double slit (FIG. 9B) and ten slits (FIG.9C).

FIG. 10 is a linear wavelength dispersion of a spherical grating

FIG. 11 show the spectral range of UVC light sources.

FIG. 12 depicts the stability of UVC light sources.

FIG. 13 shows the average irradiance of UVC sources.

FIG. 14 shows the spectrum of UVC light sources.

FIG. 15 depicts the various power requirements of UVC light sources.

FIG. 16 depicts a comparison of light source efficiency based onapplication in UVC absorption spectroscopy.

FIG. 17 depicts the expected lifetime for different types of UVC lightsources.

FIG. 18 depicts the average startup times of various UVC light sources.

FIG. 19 depicts estimated present costs of UVC light sources.

FIG. 20 provide a tunable UV type detector scheme.

FIG. 21 provides a photodiode array type detector scheme.

FIG. 22 provides an unfolded optical pathway for alternative scheme.

FIG. 23 provides an unfolded optical pathway with aperture stops.

FIGS. 24A, 24B and 24C are an embodiment of the optical layout for theUVC LED detector of the present invention.

FIG. 25 shows transmissibility versus frequency ration curve.

FIG. 26 shows an optical layout of an embodiment of the UV-LED detector.

FIG. 27 show an embodiment of the optics bench assembly.

FIGS. 28A and 28B show an embodiment of the optics bench assembly wherelocating pins have chamfer at one end to guide the insertion of a partduring assembly.

FIGS. 29A and 29B show an embodiment of the optics bench assembly. FIG.29A shows the top view of the optics bench assembly and FIG. 29B showsthe isometric view of the optics bench assembly.

FIG. 30 provides a chart of thermal conductivity for screening suitablematerials for the optics bench assembly based on thermal conductivity.

FIG. 31 provides a chart of thermal expansion versus thermalconductivity for selection of suitable material for the optics benchassembly with good dimensional stability and low thermal distortion.

FIG. 32 provides a chart of Young's modulus versus density for selectionof material with low vibration sensitivity.

FIG. 33 is a chart of Young's modulus versus strength for selection ofmaterial with high resistance to deformation during impact loads.

FIG. 34 is a chart of cost per unit weight of different materialclasses.

FIG. 35 shows an embodiment of the optics bench assembly for drop testanalysis.

FIG. 36 shows an embodiment of the optics bench assembly for drop testanalysis with wall thickness 4 mm without shock mounts.

FIGS. 37A, 37B, 37C, 37D and 37E show drop test analysis of anembodiment of the optics bench assembly with shock mounts for choosingan optimal wall thickness.

FIG. 38 is a graph depicting variation of maximum stress during impactloading and overall weight of the optics bench assembly with increasingwall thickness.

FIGS. 39A, 39B, 39C, 39D and 39E show first five vibration modes of theoptics bench assembly.

FIG. 40 is a graph depicting variation of natural frequency of opticsbench assembly in critical mode with optics bench casing wall thickness.

FIG. 41 illustrates a low frequency bubble mount vibration isolator.

FIGS. 42A, 42B and 42C is an illustration of an embodiment of the opticsbench assembly providing maximum dimensions for calculating a naturalconvection heat transfer coefficient.

FIG. 43 is an embodiment of the optics bench assembly depicting majorheat sources.

FIG. 44 is an embodiment of the optics bench assembly showing a thermalanalysis.

FIG. 45 is an embodiment of a UV-LED detector presented herein depictingthe locations of fans and air outlets for thermal management of thedetector.

FIG. 46 is an embodiment of the optics bench assembly depicting theoptics bench casing and top cover.

FIG. 47 is a process-material matrix for manufacturing process selectionof an embodiment of the optics bench assembly based on material.

FIG. 48 is a process-material matrix for manufacturing process selectionof an embodiment of the optics bench assembly based on shape.

FIG. 49 is a process-mass range chart for manufacturing processselection of an embodiment of the optics bench assembly based oncomponent mass.

FIG. 50 is a process-section thickness chart for manufacturing processselection of an embodiment of the optics bench assembly based oncomponent section thickness.

FIG. 51 is a process-tolerance chart for manufacturing process selectionof an embodiment of the optics bench assembly based on tolerancerequirement.

FIG. 52 is an economic batch size chart for manufacturing processselection of an embodiment of the optics bench assembly based oneconomic batch size.

FIG. 53 depicts cross sectional view of an embodiment of the opticsbench casing.

FIG. 54 shows a sealing gasket in an embodiment of the optics benchassembly.

FIG. 55 shows a dry gas purge filler valve in an embodiment of theoptics bench casing.

FIG. 56 is a schematic showing key dimensions of an optical layout andorientation of DMD with respect to a spectral plane of grating useful inan error budget analysis.

FIG. 57 shows resolution sensitivity with respect to manufacturingtolerances and change in temperature in the optical layout.

FIG. 58 is a schematic of an embodiment of the optics bench assemblywith dimensions to be calibrated.

FIGS. 59A and 59B show the calibration for a spherical grating.

FIGS. 60A and 60B show a prototype of the optics bench assembly.

FIG. 61 provides a pie chart showing market demand of HPLC in 2013.

FIG. 62 provides a pie chart showing percentage of monographs withliquid chromatography broken down by different wavelengths.

FIG. 63 is a schematic of a fixed wavelength detector.

FIG. 64 is a schematic of a scanning type detector.

FIG. 65 is a schematic of a photodiode array detector.

FIG. 66 shows an exemplary UV LED.

FIG. 67 shows spectral distribution of a UV LED with maxima at 260 nm.

FIG. 68 depicts an embodiment of a digital micro-mirror array.

FIG. 69 provides a functional schematic of an embodiment of the detectordescribed herein.

FIG. 70 shows functionality of the components of an embodiment of afixed wavelength detector as provided in Configuration 1.

FIG. 71 depicts a schematic of an embodiment of the detector as providedby Configuration 1.

FIG. 72 shows functionality of the components of an embodiment of afixed wavelength detector as provided in Configurations 2 and 3.

FIG. 73 is a schematic of an embodiment of the detectors provided byConfigurations 2 and 3.

FIG. 74 shows clustered design structure matrices (“DSM”) for lightinteractions.

FIG. 75 shows clustered DSM for spatial interactions.

FIG. 76 shows an embodiment of an architecture scheme for Configuration1.

FIG. 77 shows embodiments of architecture schemes for Configurations 2and 3.

FIG. 78 depicts the components of a HPLC system.

FIGS. 79A & 79B illustrates how a chromatographic column works—bands.

FIG. 80 shows an illustration of how peaks are created in the liquidchromatography system.

DETAIL DESCRIPTION

Liquid chromatography (“LC”) is a technique in analytical chemistry usedto separate, identify and quantify compounds in a mixture. Liquidchromatography techniques can be broadly classified into planar andcolumnar techniques. In both of the techniques, the sample can be firstdissolved in liquid that is then transported to a liquid chromatographysystem.

In the column technique, pressurized liquid solvent containing a samplemixture can be passed through a column 22 filled with a solid adsorbentmaterial. As the sample mixture is passed though the column 22,constituents of the mixture will interact differently with the columnabsorbent. In the mobile phase, compounds in the sample distribute orpartition differently between moving solvent. The column particles arereferred to as the stationary phase. Because constituents (also referredto herein as compounds) move at different speeds, different coloredbands relating to different compounds can be generated. Arsenault, J. etal., Beginners Guide to Liquid Chromatography, 2nd ed. WatersCorporation, 2009.

In early liquid chromatography systems, high pressure of about 35 barwas used to generate the flow in packed columns. These systems wereknown as High-Pressure Liquid Chromatography (“HPLC”). The 1970s sawimprovement in HPLC technology in developing pressures up to 400 bar andincorporating improved injectors, detectors and columns. With continuedadvances in performance with technologies such as smaller particles andhigher pressures the acronym remained the same but the name was changedto High-Performance Liquid Chromatography (also referred to as “HPLC”).Furthermore, advancements in instrumentation and column technology haveled to increases in resolution, speed and sensitivity in liquidchromatography. High performance can be achieved through the use ofcolumns having particles as small as 1.7 microns and instrumentationwith specialized capabilities can deliver the mobile phase at about 1000bar and referred to as Ultra-Performance Liquid Chromatography (“UPLC”).

Today, LC systems can identify compounds in trace concentrations as lowas parts per trillion (ppt). Many variations exist in relation to thepressure with which the solvent is pumped through the LC system, i.e.,low pressure liquid chromatography (approximately at 3 bar), highpressure chromatography (approximate 400 bar) and more recentlyultra-high pressure liquid chromatography (approximate 1000 bar). HPLCand UPLC have application in many industries including pharmaceuticals,food, cosmetics, environmental matrices, forensic samples and industrialchemicals.

In its simplest representation a liquid chromatography system comprisesfour components: a solvent pump (not shown), a sample injector (notshown), a column 22 (stationary phase), and a detector 4. A general LCprocess and set up is generally represented in FIG. 1. Sample is pumpedto the required pressure and injected into the stream of solvent. Themixture is then passed through the column 22, where the constituents ofthe sample are separated and the detector 4 is used to measure thequantity of constituent. A liquid chromatography system 2 can alsoinclude a sample manager (not shown), a solvent manager (not shown), acolumn heater (not shown) and/or a column manager (not shown). In theliquid chromatography system 2, the detector 4 is identifiesconstituents (compounds) in the mixture eluted from the chromatographycolumn 22 by measuring a light absorbing property or other property ofthe column eluent.

The components of the liquid chromatography system 2 (“LC System”) areshown in the FIG. 78. In FIG. 78, a reservoir 32 holds the solvent (alsoreferred to as “the mobile phase”). A high-pressure solvent pump 18 in asolvent delivery system (not shown) or in the solvent manager (notshown) is used to generate and meter a specified flow rate of the mobilephase, typically milliliters per minute. An injector 36 in the samplemanager 24 (also referred to as an autosampler) is able to introduce(inject) the sample into the continuously flowing mobile phase thatcarries the sample into the HPLC column 22. As noted herein, the column22 contains the chromatographic packing material (not shown) required toeffect the separation. This packing material is called the stationaryphase because it is held in place by column hardware. The sample manager24 directs flow of sample through the flow cell 66.

The detector 4 is needed to “see” the separated compound bands as theyelute from the HPLC column 22. The mobile phase exits the detector 4 andcan be sent to waste, or collected, as desired. When the mobile phasecontains a separated compound band, LC system 2 provides the ability tocollect this fraction of the eluate containing that purified compoundfor further study. This is called preparative chromatography.High-pressure tubing (not shown) and fittings (not shown) are used tointerconnect the pump 18, injector 36, column 22, and other detectorcomponents to form the conduit for the mobile phase, sample, andseparated compound bands.

The detector 4 is a component of the LC system 2 that identifies andquantitates the concentration of the sample constituents (see FIG. 78).The detector 4 records an electrical signal needed to generate thechromatogram on its display. Since sample compound characteristics canbe different, several types of detectors have been developed asdescribed herein. For example, if a compound can absorb ultravioletlight, a UV-absorbance detector is used. If the compound fluoresces, afluorescence detector is used. If the compound does not have either ofthese characteristics, a more universal type of detector is used, suchas an evaporative-light-scattering detector (ELSD). A powerful approachis the use multiple detectors in series. For example, a UV and/or ELSDdetector may be used in combination with a mass spectrometer (MS) toanalyze the results of the chromatographic separation. This provides,from a single injection, more comprehensive information about ananalyte. The practice of coupling a mass spectrometer to an HPLC systemis called LC/MS.

HPLC Operation

As shown in FIGS. 79A and 79B, mobile phase enters the column 22 fromthe left, passes through the particle bed, and exits at the right. Flowdirection is represented by the arrows. As shown in G1, the column 22 attime zero (the moment of injection) when the sample enters the column 22begins to form a band. The sample shown here, a mixture of yellow, red,and blue dyes, appears at the inlet of the column 22 as a single blackband. In practice, this sample could be anything that can be dissolvedin a solvent. Typically, the compounds would be colorless and the column22 wall opaque, so the detector 4 is needed to see the separatedcompounds as they elute. After a few minutes, during which mobile phaseflows continuously and steadily past the packing material particles, wecan see that the individual dyes have moved in separate bands atdifferent speeds. This is because there is a competition between themobile phase and the stationary phase for attracting each of the dyes oranalytes. Notice that the yellow dye band moves the fastest and is aboutto exit the column 22. The yellow dye likes (is attracted to) the mobilephase more than the other dyes. Therefore, it moves at a faster speed,closer to that of the mobile phase. The blue dye band likes the packingmaterial more than the mobile phase. Its stronger attraction to theparticles causes it to move significantly slower. In other words, it isthe most retained compound in this sample mixture. The red dye band hasan intermediate attraction for the mobile phase and therefore moves atan intermediate speed through the column 22. Since each dye band movesat different speed, we are able to separate it chromatographically.

As the separated dye bands leave the column 22, they pass immediatelyinto the detector 4. The detector 4 contains a flow cell 66 that sees ordetects each separated compound band of the mobile phase (FIG. 80). Asnoted above, solutions of many compounds at typical HPLC analyticalconcentrations are colorless. The detector 4 has the ability to sensethe presence of a compound and send its corresponding electrical signalto a computer data station 27. A choice can be made among many differenttypes of detectors 4, depending upon the characteristics andconcentrations of the compounds that need to be separated and analyzed,as discussed herein.

A chromatogram is a representation of the separation that has chemically(chromatographically) occurred in the LC system 2. A series of peaksrising from a baseline is drawn on a time axis. Each peak represents thedetector 4 response for a different compound. The chromatogram isplotted by the computer data station 27. (FIG. 80). In FIG. 80, theyellow band has completely passed through the flow cell 66; theelectrical signal generated has been sent to the computer data station27. The resulting chromatogram has begun to appear on screen of thecomputer data station 27. Note that the chromatogram begins when thesample was first injected and starts as a straight line set near thebottom of the screen. This is called the baseline; it represents puremobile phase passing through the flow cell 66 over time. As the yellowanalyte band passes through the flow cell 66, a stronger signal is sentto the computer. The line curves, first upward, and then downward, inproportion to the concentration of the yellow dye in the sample band.This creates a peak in the chromatogram. After the yellow band passescompletely out of the detector cell, the signal level returns to thebaseline; the flow cell 66 now has, once again, only pure mobile phasein it. Since the yellow band moves fastest, eluting first from thecolumn 22, it is the first peak drawn.

When the red band reaches the flow cell 66, the signal rises up from thebaseline as the red band first enters the cell, and the peakrepresenting the red band begins to be drawn. In this diagram, the redband has not fully passed through the flow cell 66. The diagram showswhat the red band and red peak would look like if the process wasstopped at this moment. Since most of the red band has passed throughthe cell, most of the peak has been drawn, as shown by the solid line.If the process is restarted, the red band completely passes through theflow cell 66 and the red peak would be completed (dotted line). The blueband, the most strongly retained, travels at the slowest rate and elutesafter the red band. The dotted line shows a completed chromatogram uponconclusion of testing. Note that the width of the blue peak will be thebroadest because the width of the blue analyte band, while narrowest onthe column 22, becomes the widest as it elutes from the column 22. Thisis because it moves more slowly through the chromatographic packingmaterial bed and requires more time (and mobile phase volume) to beeluted completely. Since mobile phase is continuously flowing at a fixedrate, this means that the blue band widens and is more dilute. Since thedetector 4 responds in proportion to the concentration of the band, theblue peak is lower in height, but larger in width.

Currently, liquid chromatography can utilize a detector 4 differentclasses including: (1) bulk property detectors, and (2) specificproperty detectors. Bulk property detectors measure the bulk physicalproperty of the column 22 discharge and specific property detectorsmeasure a physical or chemical property of the solute. Bulk propertydetectors include a refractive index detector, an electrochemicaldetector, and a light scattering detector. Specific/solute propertydetectors include a UV-Visible light detector, fluorescence detector andmass spectroscopic detector.

TABLE 1 Different Types of Liquid Chromatography Detectors Bulk PropertyDetectors Specific/Solute Property Detectors Refractive Index DetectorUV-Visible Light (Absorbance Detector) Electrochemical DetectorFluorescence Detector Light Scattering Detectors Mass SpectroscopicDetector

UV-Visible Light detectors are specific/solute property detectors whichoperate in the UV and visible light spectrum by either using filters toget a specific wavelength or by splitting the incident light (using aprism or diffraction grating) from the light source before or after ithas passed the sample. Intensity is measured after light has gonethrough the sample to calculate absorbance of the sample. Absorbancedetectors can be further subdivided into two categories including fixedwavelength detectors and variable wavelength detectors. Fixed wavelengthdetectors use a narrow band pass optical filter to get monochromaticlight from the source and therefore do not need to split the light.Variable wavelength detectors 4 split light into its constituentspectrum using a prism/diffraction grating. Variable wavelengthdetectors 4 include both scan and photodiode array detectors 254.

In UV scan detectors, either the photo-detector or the prism/diffractiongrating 14 is moved via motors to allow for potentially monitoring thesample at each separate wavelength. A Tunable UV (“TUV”) detector can bea tunable, dual-wavelength UV/Visible detector. Because of the inertiaof the grating 14 and motor mechanism, at high speeds, switching betweenwavelengths at high speeds is not available.

In a photodiode array detector 254, referred to herein sometimes as “PDAdetector,” light after passing through the sample is split into itsconstituent wavelengths and are made incident on an array of photodiodesto allow the simultaneous monitoring at many different wavelengths.

As shown in FIG. 2A, the detector 4 provided herein is compatible foruse in a liquid chromatography system 2 (“LC system”), particularly foruse in an HPLC systems and UPLC systems. The detectors 4 provided hereincomprise a light delivery system 110 having a light source 50, awavelength selection module 140 comprising a digital micro-mirror device8 (“DMD”), the flow cell 66 and a light detection unit 190. As notedherein, the detector 4 can be compatible with other liquidchromatography systems 2 including UPCC (or Supercritical FluidChromatography) or even in non-chromatographic applications such asmonitoring process fluids in industrial processes.

With reference to the Figures, FIGS. 2A and 2B depict detectors of thepresent disclosure which can optically interrogate the contents of aflow cell 66. In the figures, dashed line arrows will indicate fluid orsample flow while block arrows denote light paths (sometimes referred toas light pathways. The difference between the systems in FIGS. 2A and 2Bis the location of the flow cell 66. In FIG. 2A, the flow cell 66follows the wavelength selection module 140. In FIG. 2B, the flow cell66 precedes the wavelength selection module 140. There can be functionaldifferences between the wavelength selection modules 140 and the flowcell 66 in both configurations.

The main difference between the two schemes of FIGS. 2A and 2B isdescribed herein. Typically the wavelength selection module is placedafter the flow cell in applications where the entire wavelength spectrumcan be probed simultaneously. By contrast, this wavelength selectionmodule is placed before the flow cell if the analyte to be identified isphotosensitive, to minimize stray light, and to probe the opticalproperties at a single wavelength of interest. The latter may includefluorescence, specific absorption or refractive index measurement. Ineach case, the flow cell can be optimized to measure either thetransmission (absorption), out of axis radiation (fluorescence) or beamsteering (refractive index).

As described herein, the detector 4 can comprise an optics benchassembly 40 that comprises both optical components and structuralcomponents (combined sometimes referred to as the “optics bench assemblycomponents”). Optical components of the optics bench assembly 40 canhave: (1) an entrance slit 12 for light received by the detector 4; (2)a grating 14; (3) a digital micro-mirror device (“DMD”) 8; (4) aspherical convex mirror 56; (5) a beam splitter 60; (6) a referencephotodiode 62; (7) a main photodiode 64; and (8) a flow cell 66.

The structural components of the optics bench assembly 40 describedherein can include: (1) a light dump 54 (sometimes referred to herein asa “light dump/shield” or a “light shield”); (2) an optics bench assemblycasing 44; (3) an optics bench assembly cover 70; (4) a mirror 56, (5) agrating mounting mechanism 71; (6) a plurality of mounting brackets 72and (7) a plurality of fasteners. 73

Depending upon the light source 50 of the light delivery system 110, itmay be desirable to have the flow cell 66 placed after the wavelengthselection module 140 in the optics bench assembly 40. For example, ifthe output of the light source 50 is broad band and includes wavelengthsthat may induce undesirable photochemical responses within the sample.Pre-filtering these wavelengths with the wavelength selection module 140will insure that that the interrogated sample species is not alteredfrom that which was delivered to the flow cell 66. As described herein,a suitable light source 50 includes various discharge lamps, such asdeuterium or xenon lamps as well as composite light sources in whichindividual emitters such as a plurality of light emitting diodes(“LEDs”) are so arranged to provide a range of wavelengths, eachrepresenting the center emission wavelength of one LED 6. An output ofthe light source 50 can be essentially monochromatic, such as from alaser, or a narrow band UV LED 6, or a discharge lamp emitting only afew spectral lines. The output of the light source 50 may be intense, inwhich case, the wavelength selection module 140 can comprise an opticalattenuator (not shown). By having the flow cell 66 follow the wavelengthselection module 140 (as in FIG. 2A), the wavelength of interest can beselected or tuned to match the spectral absorption features of theanalyte of interest. In this case, wavelength selection can beaccomplished through the use of a motorized mechanism which controls theangular position of a dispersing element such as a grating 14.

FIG. 3A provides a block diagram of the wavelength selection module 140incorporating a grating 14. The entrance slit 12 defines a narrow widthof an incident light beam 138 and sets the smallest achievableresolution by setting the image resolution at the detector plane, or howmuch wavelengths will overlap given a fixed exit slit, or pixel width.The optical resolution is inversely proportional with the exit slitwidth and typically ranges between 0.01 nm and 20 nm. Beyond theentrance slit 12, a first light beam 146 is collimated by a reflectingmirror 56 and is redirected as a second light beam 152 a towards a planereflective grating 14 where it is diffracted into its constituentcolors. By rotating the grating 14 to specific angles, the wavelength ofinterest will be redirected as a third light beam 152 b towards anoutput focusing element 52 that redirects a fourth light beam 166 to anexit slit 68. Some portion of the fourth light beam 166 incident at theexit slit 68 can be redirected as a fifth light beam 164 towards areference detector 38 with the aid of a beam splitter 162, which may beas simple as a window transparent to all wavelengths of interest.

The rotation (in both directions) of the plane reflective grating 14 isabout an axis perpendicular to the plane of FIG. 3A, as signified by thecurly arrow. A sixth light beam 168 exiting through the exit slit 68 isdirected towards the flow cell 66. After passage through the flow cell66, the sixth light beam 168 can be converted to an electric signal by alight detection unit 190. In this configuration, light detection unit190 can include transfer optics (not shown) to efficiently couple thelight leaving the flow cell 66 to a single photodiode detector or a typesimilar to the reference detector 38.

Use of the reference detector 38 is beneficial in compensating forcommon-mode variations in light intensity that could otherwise confusethe interpretation of the signal from the light detection unit 190. Forexample, a reduction in light output from 110 of 1% could decrease thesignal of the light detection unit 190 by substantially the same amount;if not compensated, this decrease would be interpreted by an absorbancedetector (not shown) as an increase in concentration of the analyte.However, the reference detector 38 can report a similar decrease, andthrough signal ratio, eliminate the reporting of a false positive (ornegative) analyte concentration.

In array detectors, the flow cell 66 preceding wavelength selectionmodule 140 enables simultaneous detection of light at many wavelengths,without having to physically move a dispersing element (i.e., grating).A typical layout of such wavelength selection module 140 is shown inFIG. 3B. A first light beam 138 exits the flow cell 66 and passesthrough the entrance slit 12 and an emergent light beam 246 is collectedby a concave grating 14, which both disperses and images the diffractedwavelengths into a single focal plane where an array detector 254 islocated. Here, the array detector 254 is typically a linear array ofpixels although 2D-imaging array or fiber bundle can also be employed. Agiven pixel may be between 10 to 200 microns wide and from 10 to 2500microns tall. Two dispersed light beams 252 a, 252 b leaving an imaginggrating 14 are illustrating the constituent colors or wavelengths of theemergent light beam 246 that have passed through the entrance slit 12and are imaged at different locations along the array detector 254.Thus, the dispersed light beam 252 a can correspond to a shortwavelength and the dispersed light beam 252 b to a longer wavelength.The mechanical width of the entrance slit 12 influences spectralresolution, basically establishing the minimum width of the focusedcolors at the array and how many pixels correspond to this width. Forexample, an entrance slit width of ˜100 microns could result in imagewidths of similar size at the array detector 254; the height of thisimage depending upon how much of the entrance slit height is illuminatedby light beam 138 as well as the mechanical height of each pixel. Theilluminated height of the entrance slit 12 might range from tens ofmicrons to several millimeters.

Certain advantages offered by each of the two methods (of differing flowcell location with respect to the wavelength selection module) can berealized with the incorporation of a digital micro-mirror array. Inparticular, the substitution of a digital micro-mirror array for thearray detector 254 and followed by the flow cell 66 and light detectionunit 190 can avoid potential issues associated with intense lightsources yet permit tunability by eliminating a mechanical grating drivesystem and grating 14, replacing it with the highly reliable beamsteering capabilities of the digital micro-mirror array. In the detector4 described herein, the digital micro-mirror device 8 (“DMD”) isemployed to redirect selected regions of a focused light spectrum to anoptical output pathway which is connected to a flow cell 66.

Referring now to FIG. 4, a light delivery system 110 directs a broadspectrum light beam 338 at an entrance slit 12 of a wavelength selectionmodule 140 to generate the optical output pathway. After passage throughthe entrance slit 12, an incident light beam 346 is incident upon aspectrum dispersing element 350 to form a plurality of focused beams ofconstituent colors 352 a, 352 b at the DMD 8. By selective control ofthe micro mirrors (not shown), the focused beams of constituent colors352 a, 352 b on the DMD 8 can be sent in two directions. One directionrepresented by a first reflected beam 358 a along the optical outputpathway that leads to an output beam 358 employed for subsequentanalytical purposes such as transmission into the flow cell 66. Thesecond direction represented by a second transmission beam 358 bcorresponding to transmission along the optical output path toward alight dump 54 that absorbs all incident light or alternatively to asecondary analytical pathway similar to the first reflected beam 358 abut at a different wavelength. The first reflected beam 358 a is firstincident upon an optical output subsystem 360 that can includebeam-shaping elements for controlling the shape and direction of anoutput beam 358 in the optical output pathway. An intensity referencingsystem (not shown) can be inserted after the optical output subsystem360 for providing a reference light beam 364 with the aid of a partialreflecting element 362 and the reference detector 38.

The optical output subsystem 360 can refocus the spatially resolvedcolors at the DMD 8 into distinct locations at an output focus point ofthe optical output beam 358 and in the optical output pathway. Thus, theoptical output subsystem 360 can be a simple lens, a reflecting mirroror an aspheric surface such a reflecting ellipse or lens. As shown inFIG. 5A, spatially resolved colors at the DMD 8 such as a first outputbeam 358 a-1 or a second output beam 358 a-2 are imaged to output beamlocations as an imaged output beam 358-1 and an imaged output beam358-2, respectively. Here, individual rays within the beam leaving theDMD 8 are shown in conventional fashion with an arrowhead indicatingdirection of travel; one pair of rays is shown as dot-dashed lines todistinguish it from the other pair. In this configuration, the differentcolors are focused into distinct images, each of which can beselectively turned on and off and directed to various flow cells thatcan operate at different analytical wavelengths. It may also bebeneficial in some cases to employ a field lens (not shown) as a coverslip for the DMD 8; the optical power of the field lens is chosen toimage the clear aperture of element 358 onto element 360-1, therebyretaining a compact beam size at this element.

In another configuration, the optical output subsystem 360 can compriseof several elements which function to recombine all focused colors atthe DMD 8 into a single image at the output focus of beam 358. Again,omitting the reference channel components for clarity, FIG. 5B depictsone combination of elements to achieve this objective. A first lens360-2 collimates the beams diverging from the DMD 8; these constituentcollimated beams are incident upon a transmission grating 360-3. Theangles of incidence at the grating vary with wavelength or color.Through grating spacing and incidence angles, the diffracted beamstransmitted through the grating 14 are rendered parallel to one anotherand may be brought to a common focus by a second lens 360-4. The commonoutput focus for all colors comprising the beam leaving the DMD 8 isdenoted 358-X. A single focal point for all colors is advantageous interms of minimizing the size of the input face of the flow cell 66,leading to small flow cell volumes, and can be advantageous fordetecting narrow peaks eluting from small bore or capillary scale liquidchromatographic columns 22. Use of a field lens on DMD 8 can also assistin maintaining a compact beam size through components comprising thisvariation of the output optical system.

Other combinations for the detector 4 include the DMD 8 as the entranceslit or exit slit. In this configuration, each of the mirrors of the DMD8 acts as an on/off switch by directing the light either to a beam dumpor to the subsequent optical elements. The number of on-element in thehorizontal and the vertical direction will define the width and theheight of the variable slit and can be dynamically assigned. At theinput side, the DMD 8 will define the size of the object, which canimpact the imaging resolution and optical throughput. At the outputside, the DMD 8 would define the spectral bandwidth being analyzed by asingle element detector 4 in an analogous way to pixel bunching inimaging array.

Typically, the optical coupling is optimized to fill the lumen of theflow cell 66 to increase the optical throughput. Having a concentriclong or short path flow cell design, the light intensity distributioncould be shaped to have most of the light entering in the centralportion (long pathway) with some residual light going into the outerportion to increase the dynamic range of the measurement. Alternatively,an abberrated or oversized image at 358-X can be used for distinct flowcells (long/short path).

Relevant Optical Theory Snell's Law: Index of Refraction

For any transparent medium, the index of refraction for that medium,η_(m), is defined as the speed of light in a vacuum, c, divided by thespeed of light within that medium, c_(m), as shown. Peatross, J. W. P.,Physics of Light and Optics, 2008.

$\begin{matrix}{\eta_{m} = \frac{c}{c_{m}}} & (1)\end{matrix}$

Snell's Law describes the way light is transmitted at the interface oftwo mediums. As seen in FIG. 6, light will bend when passing betweenmediums which have different indices of refraction. This phenomena isdescribed by Snell's law, given in Equation 2, where the ratio of thesines of the incident and transmitted angles is equal to the ratio ofthe indices of refraction in the two mediums. Id.

$\begin{matrix}{\frac{\eta_{t}}{\eta_{i}} = \frac{\sin\mspace{11mu}\theta_{i}}{\sin\mspace{11mu}\theta_{t}}} & (2)\end{matrix}$

Snell's Law: Total Internal Reflection

By solving Snell's law for θ_(t) as shown in Equation 3, a criticalangle θ_(c) at which θ_(t) becomes imaginary, is provided by Equation 4.

$\begin{matrix}{\theta_{t} = {\sin^{- 1}\left( {\frac{\eta_{t}}{\eta_{i}}\mspace{14mu}\sin\mspace{14mu}\theta_{i}} \right)}} & (3) \\{\theta_{c} = {\sin^{- 1}\left( \frac{\eta_{t}}{\eta_{i}} \right)}} & (4)\end{matrix}$All light incident at or below the critical angle will reflectcompletely without any transmission through the second medium. Thiseffect allows optical fibers to transmit light over large distances oralong a specific pathway with little loss, as shown in FIG. 7.

Numerical Aperture

The numerical aperture (“NA”) of an optical element is a dimensionlessnumber which is defined in Equation 5, as the refractive index of themedium, n, times the sine of the half angle of the element's acceptancecone, α. B. Wolf, Principles of Optics, 1970. The numerical aperturesquared may be thought of as the light gathering power of the element.NA=n sin α  (5)

In FIG. 8, we can see what happens when we couple two optical elementstogether which have mismatched numerical apertures. Working through theoptical system in one direction, the second element of the pair will beoverfilled and the extra light will be unable to propagate through therest of the system properly. If, instead, we start from the otherdirection the second element will be under-filled. The couplingefficiency, or fill factor, for the second element will be the ratio ofsquares of their numerical apertures as shown in Equation 6.

$\begin{matrix}{\eta_{coupling} = {\frac{{NA}_{element}^{2}\mspace{11mu}}{{NA}_{source}^{2}} = F_{element}}} & (6)\end{matrix}$

Etendue

The etendue of a detector can be defined in Equation 7, as the crosssectional area of the source, A_(s) times the solid angle through whichthe light propagates, Ω. It can be thought of as the ability of anoptical system to accept light.ε=A _(s)Ω  (7)

For small solid angles, Ω will be linearly proportional to the numericalaperture squared and the expression for etendue can be written as shownin Equation 8. Peatross, J. W. P., Physics of Light and Optics, 2008.ε=A _(s) πNA ²  (8)

Optical Power

Having the etendue, the flux, ϕ, or optical power, passing through itcan be calculated by simply taking the product of the Etendue and theradiance of the source, as shown in Equation 9. Id.ϕ=εR  (9)

Fraunhofer Single Slit Diffraction

When coherent light passes through a narrow slit in a plane normal tothe light's Poynting vector, it produces interference patterns which inthe far-field are well described by the Fraunhofer diffraction equation,given in Equation 10. B. Wolf, Principles of Optics, 1970.

$\begin{matrix}{I = {I_{o}\left( \frac{\sin\mspace{11mu} x}{x} \right)}^{2}} & (10)\end{matrix}$Where I is the intensity, I_(o) is the intensity at the center of thediffraction pattern, and with minima occurring wherever x is an integermultiple of π. Id.

Grating Theory

If more than one slit are arranged in a pattern, the effects of theinterference are compounded. As shown in FIGS. 9 and 10, with moreslits, the peaks become taller and narrower. Because the location of thepeaks is dependent upon the wavelength of diffracted light, this effectcan be used to sort light based on wavelength. If a repeating pattern ofgrooves is used in a reflective surface rather than slits, more of theoptical power is retained. Such an optical element is called areflective grating 14. The diffraction off of such a grating isdescribed by the grating equation, as shown in Equation 11:sin α+sin β=knλ  (11)

Where α is the incident angle, β is the diffracted angle, k is the orderof diffraction, n is the groove density, and λ is the wavelength. FromEquation 11 and the geometry shown in FIG. 10 an expression for thelinear dispersion of a spherical grating can be derived in nanometersper millimeter, which is provided in Equation 12 below:

$\begin{matrix}{\frac{d\;\lambda}{dx} = \frac{10^{6}\mspace{11mu}\cos\mspace{11mu}\beta\mspace{11mu}\cos^{2}\;\gamma}{{knL}_{H}}} & (12)\end{matrix}$

Digital Micro-Mirror Devices

As provided herein, the detector 4 comprises a digital micro-mirrordevice (“DMD”) 8 and a light source 50. In an embodiment, one or moreUltraviolet Light Emitting Diode (“UV-LED”) 6 can be provided as thelight source. Alternatively, the light source 6 can be a deuterium lampor a zeno lamp. As described herein, an optics bench assembly 40 havingcertain structural components on which the optical components of thedetector 4 are mounted.

DMD 8 is an opto-electro-mechanical device that is smaller and lighterthan current mechanical gratings used in liquid chromatography systems.DMD 8 can be used in combination with a diffraction grating to separatelight of different wavelengths into finer resolution and at a far higherfrequency. The detector 4 having both UV-LEDs 6 and DMD 8 can have amodular architecture, where LEDs can be replaced with relative ease.

The digital micro-mirror device 8 contains arrays of thousands tomillions of microns scale mirrors fixed to mems actuators which alloweach individual mirror to be positioned at either ±θ° from its neutral“flat” state. This allows arbitrary patterns of light to be imaged athigh speeds. For a photodiode the shot noise power which arises from thequantized nature of light, is given by Equation 13.

=2qB(I _(signal) +I _(dark))  (13)

Where q is the charge of an electron, B is the measurement bandwidth inHz, and I is current. If we assume that dark current is much smallerthan the signal current and solve for the root mean square we can findthe shot noise in the current coming out of the photodiode, as shown inEquation 14.i _(n) _(rms) ≅√{right arrow over (2qBI _(signal))}  (14)

By dividing the signal current by this expression we can find the signalto noise ratio, SNR, for a system dominated by shot noise, given inEquation 15.

$\begin{matrix}{{SNR}_{sn} = \sqrt{\frac{I_{signal}}{2{qB}}}} & (15)\end{matrix}$The signal to noise ratio is proportional to the square root of thesignal strength.

Light Source Selection

The Ultra Violet (“UV”) emitting light source 50 includes various gasarc lamps and hot filament lamps, such as deuterium arc lamps, mercuryarc lamps, xenon flash lamps, quartz and tungsten halogen lamps, and UVCLEDs. LEDs can be employed singly, such as a 250 nm LED 6 or combinedinto groups, such as for example 11 LEDs with center wavelengths from220 nm to 320 nm. Many factors are considered when selecting a lightsource 50 for UV absorption spectroscopy including the spectral rangeemitted by the source, total irradiance (or optical power output) andits spectral distribution, output stability, efficiency, lifetime,startup time, and the cost of the light source.

As shown in FIG. 11, the spectral range emitted by a light source 50sets the limits for the wavelengths at which a spectrometer can detectabsorption. In UV absorption spectroscopy, the signal is a decrease inintensity of the light exiting the flow cell 66 caused by sampleabsorption. As a result, the process is extremely sensitive to shortterm fluctuations in the intensity of the light source. In FIG. 12, thestability of various light sources for each type and shows deuteriumlamps and LEDs has a similar level stability which is two orders ofmagnitude better than any of the other sources.

With regards to optical power and spectral irradiance, Beer's lawinforms that when the light throughput of the flow cell 66 is increased,at some point the sample will saturate and be unable to absorbadditional light. Therefore, arbitrarily increasing light throughputdoes not always aid in detection. In fact, it can make detection moredifficult. If the steady state throughput is many orders of magnitudehigher than signal, the sensor and associated electronics will saturateif they have to small a small dynamic range, or if a large dynamic rangeis used, it could lack the sensitivity of a sensor with a much smallerdynamic range. Vickrey, T. M., Liquid Chromatography Detectors, Vol. 23.CRC Press, 1983. However, if the geometry of the flow cell is varied, wewill notice that the etendue and, thus, the optical power throughputscales as the diameter of the flow cell squared, as shown in Equations 8& 9.

Reducing the diameter of the flow cell 66 reduces the minimum samplevolume required by the same factor squared, assuming the same absorptionlength is maintained. Therefore, optical throughput can be increasedproportionally when reducing flow cell volume to maintain the same levelof signal. As a result, the optical power provided by a source sets alower bound on the volume of flow cell in conjunction with that source.In FIG. 13, we can see the average spectral irradiance, or optical powerper nanometer of bandwidth across the UVC spectrum typical for each typeof light source.

As shown in FIG. 13, shows average UVC irradiance at 50 cm. Hightemperature, broadband light sources often have high sensitivity totemperature changes and are typically designed to have a singleoperating point. AlN LEDs exhibit little change to their peak wavelengtheither from temperature changes or when increasing or decreasing theirdriving current. As a result, we can easily modulate the irradiance ofthe LEDs by changing their driving current without adversely affectingtheir spectral output. FIG. 14, shows a small handful of representativeirradiance spectrum of the various light sources.

As shown in FIG. 15, there is a range of power requirements for eachtype of light source. All UVC light sources have relatively small wallplug efficiencies so all of its power can be assumed to effectively bedissipated as heat. Traditionally the light source 50 can havesignificant heat output, 10s to 100s of Watts, managed in such a waythat it does not adversely affect the sample or the spectrometer. Oftenthis fact drives large facets of product architecture for existingdetectors, driving their size, overall power requirements, andeliminating any possibility of portability.

Determining efficiency that can fairly and equally apply to all lightsources is not straight forward. The approach presented herein is basedon UVC absorption spectroscopy. Selectable wavelength detectors tend tohave a bandwidth of 5 nm. Therefore, to compare the efficiency of thesesources, as shown in FIG. 14, the total optical power output between 250nm and 255 nm is estimated from each spectral irradiance curve anddivided that number by the respective input power. The result is theapproximate efficiency of each type of source as it would be used forUVC absorption spectroscopy. (FIG. 16).

Although the efficiency of an array of LEDs is comparable to that of aMercury arc lamp or a Xenon flash bulb, the benefit of each is that theindividual wavelengths can be turned off and on again as needed. Thisgives LEDs an advantage of at least two orders of magnitude in rawefficiency over any other source. When adding in the ability for all ofthem to be turned off when they are not actually being sampled, theyhave the potential to improve their effective efficiency by another twoorders of magnitude over all traditional sources other than Xenon flashbulbs.

Lifetime of the light source 50 can be defined as the average time ittakes for the peak irradiance of the source to fall to half its initialvalue. FIG. 17 charts the range of expected lifetimes for each type ofUVC light source. The lifetime for a typical traditional UV lamp is 2000hours. The lifetime for a UVC AlN LED starts around 3000 hours if it isrun continuously at its maximum drive current. However, if the drivecurrent is lowered from 100 mA to 20 mA, its expected lifetime goes upto 8000 hours. The tradeoffs these LEDs exhibit between lifetime, age,drive current, and irradiance could be harnessed by creating an activedriver for each LED which gradually increases the drive current providedas it ages. Such a light source would have a consistent irradiancethroughout its lifetime, a strong signal at the end of its life, and asignificantly extended lifetime compared to a light source which startedat a higher brightness and decayed steadily to half intensity over itslife. These tradeoffs have a great deal of potential for otherapplications such as a software widget for the detector which allows theuser to adjust the drive current themselves. In this way, one devicecould equally well serve customers who want the higher brightness evenif it means replacing a lamp every 500 hours, as well as, customers whowanted to stretch out the life of their lamp and live with less signal.

Similarly, the average startup times for the various light sources isprovided in FIG. 18. For most of the lamps, the startup time is when thelamp reaches thermal steady state, and thus maximal optical stability.For the Xenon flash bulbs and the LEDs it is the rise time to achieveapproximately full brightness. The startup time of the light source isone factor impacts both the lifetime and the efficiency of the system.When the light source 50 requires a longer startup time it is consumingmore energy, none of which is usable for absorption spectroscopy. Thislowers its overall efficiency. It is also using up minutes of itslifetime which reduces its effective lifetime for detection. Theseeffects are compounded when considering user behavior. Long startuptimes prompt users to start up the machine well in advance of when theywant to start using it, and it encourages them not to shut it off forshort-duration breaks in running samples. These behaviors furtherexacerbate the reduction in overall efficiency and effective lifetime.

Finally in the selection of the light source 50 and power supply (notshown), an important factor is the relative cost of each light sourceand its power supply, which in some cases costs more than the lightemitter itself. To approximate the relative cost of the light sourcesshown in FIG. 19, we assume that each can be purchased for one tenth itsretail unit value when purchased wholesale in production quantities. Thearray of LEDs currently exceeds the cost of any traditional lightsource. However, when comparing the current cost for these lightsources, it is important to consider the differences in the product lifecycle stage between the LEDs and the other sources. While certaintraditional light sources are moderately mature technologies, AlN basedLEDs have only been commercially available for a few years. For newproduct development, it is important to keep in mind that this graph islikely to look different three to five years from now.

UVC LED

The LED 6 (sometimes referred to as “UVC LED”) produces light by takingadvantage of the bandgap in semi-conductors. Electrons in asemi-conductor junction are electrically excited across its bandgap andsubsequently de-excite, radiating light in the process. The wavelengthof light emitted by an LED is determined by its bandgap. To create LEDswhich emit at lower wavelengths requires semiconductors with largerbandgaps. Group III nitrides have bandgaps from 2 to 6 eV which makethem ideal candidates for LEDs emitting UV radiation. Ponce, et al.,Nitride-based Semiconductors for Blue and Green Light-emitting Devices,Nature, Vol. 386, No. 6623, 351-359, 1997. AlN has a particularly broadbandgap, 6.1 eV, making it ideally suited for the construction of lowwavelength LEDs. In 2006, researchers from NTT Basic ResearchLaboratories were able to develop a PIN type AlN LED with an emissionwavelength of 210 nm. Taniyasu, et al., An Aluminium NitrideLight-emitting diode with a Wavelength of 210 Nanometres, Nature, Vol.441, No. 7091, 325-328, 2006.

As AlN LEDs emitting lower wavelengths have been developed, defects inthe crystalline structure have become a prominent problem. Defects canprovide pathways for electrons to relax thermally without radiating. Asa result, the efficiency and light output of an LED 6 go down while itsheat output goes up. Many AlN LEDs are built upon a substrate of eitherSilicon Carbide or Sapphire. Mismatch between the crystal lattices ofAlN and these substrate lead to dislocation densities of 108 to 1010defects per square centimeter or even higher. Taniyasu, et al., AnAluminium Nitride Light-emitting diode with a Wavelength of 210Nanometres, Nature, Vol. 441, No. 7091, 325-328, 2006; Rojo, G., Reporton the Growth of Bulk Aluminum Nitride and Subsequent SubstratePreparation, J. Cryst. Growth, Vol. 231, No. 3, 317-321, 2001; Muramoto,Y. et al., Development and Future of Ultraviolet Light-emitting Diodes:UV-LED Will Replace the UV Lamp,” Semicond. Sci. Technol., Vol. 29, No.8, 084004, 2014

UV LED chips grown on single crystal AlN and the substrate itself havenearly identical lattice structures and therefore dislocation densitiesof only 103 to 104 defects per square centimeter is possible, atremendous improvement over LEDs grown on other substrates. Rojo, G.,Report on the Growth of Bulk Aluminum Nitride and Subsequent SubstratePreparation, J. Cryst. Growth, Vol. 231, No. 3, 317-321, 2001. LED chipsources have viewing angles of 120° or more which gives them extremelylarge numerical apertures, NA=0.87 for 120°. Crystal Is, Crystal IS SMDUVC LED, 1-8. This presents a challenge when coupling to UV transmittingoptical fibers which have numerical apertures of about 0.28. Bell etal., Multimode Fiber, Vol. 10, 1-20, 2005. Assuming the diameter of thefiber is larger than the diameter of the source (LED chip) and notincluding Fresnel losses, the theoretical maximum coupling efficiency asgiven by Equation 6 is 6.4 percent. However, use of specially designedrefractive-reflective micro lenses have the potential to increase thecoupling efficiency, raising it as high as forty percent. If instead weassume the use of such a micro lens, we can assume a coupling efficiencyof twenty percent. Rooman, C., Reflective-refractive Microlens forEfficient Light-emitting-diode-to-fiber Coupling, Vol. 44, September2005, 1-5, 2015.

Wavelength Selection

UV absorption spectroscopy detectors 4 for liquid chromatography can begrouped into three major groups: (1) single wavelength detectors such asmodels based on a mercury arc lamp line; (2) tunable UV detectors and(3) photodiode array detectors 254 b. Tunable UV and photodiode arraydetectors can both implement a strategy to distinguish betweenabsorption at different wavelengths of light.

Tunable UV detectors use a rotating planar grating and a bandwidthaperture to select wavelengths of light for detection. As shown in FIG.20, light passes through an entrance slit 12 onto a mirror 56 whichfocuses the light onto the grating 14. The light is diffracted from thegrating 14 and bounces off a second mirror 56 which focuses the lightthrough a bandwidth aperture onto the flow cell 66. Detectors 4 of thistype tend to have a fixed bandwidth of 5 to 10 nm. In a tunable UVdetector 4, only one small section of the spectrum is sent through thesample at a time. This greatly reduces the possibility of noise frommultiphoton interaction events. It allows the complete light signal tobe referenced immediately before passing through the sample which cannoticeably increase the signal to noise ratio.

Because these detectors use motors to rotate their gratings, they arenot able to dynamically switch between wavelengths in any meaningfulway. Fixed width apertures also do not permit any flexibility in thebandwidth sent through the flow cell. On the other hand, photodiodearray detectors 4 direct the light from the light source 50 straight tothe flow cell 66, sending through the entire spectrum. After the lightexits the flow cell 66 it is directed through a narrow exit slit 68 ontoa concave grating 214. The grating 14 diffracts and focuses the lightonto an array consisting of at least several hundred photodiodes. SeeFIG. 21.

Photodiode array detectors collect absorption data for the entirespectrum at one time. Obtaining the overall spectral response of asample can be a powerful analytical method, especially compared togathering information about only a single wavelength for each samplerun. These detectors still reference the optical signal, however, sincethe reference pulls from the entire spectrum at once it cannot eliminateas much noise as the reference in a tunable UV detector can. Multiphotonabsorption is a second order effect, nevertheless it has been observedin liquid chromatography detectors. Vickrey, T. M., LiquidChromatography Detectors, Vol. 23. CRC Press, 1983. By sending throughthe entire spectrum at once we lose the ability to de-convolvemultiphoton absorption and any other higher order interaction effectsfrom the conventional absorption signal.

EXAMPLE I UVC Led Detector Optical Pathway

Provided herein is a strategy for an optical pathway for a LED detectorthat allows dynamic manipulation of both the bandwidth and the specificwavelengths passed through the sample during detection. Using thisstrategy, light from one or more LED 6 may be coupled to one or moreoptical fibers, which terminate at the entrance slit to the opticsbench. Light entering the slit will be incident upon a sphericalgrating, which will diffract the light across the breadth of a digitalmicro-mirror device. Once the light is spread across the DMD 8 in thisfashion, selecting the optical bandwidth and center wavelength becomes amatter of tilting those columns of mirrors to the on position. Asdescribed and shown in FIG. 4, from the DMD 8, the selected light willbe reflected by a focusing mirror through a beam splitter and the flowcell 66 to arrive at the reference and sample photodiodes.

In FIG. 22, the unfolded optical pathway, orthogonal directions, and NAlabeled are shown. Once the various components have been defined andoptically located, they can be packaged to permit a compact footprintfor implementation in a consumer version of the detector. An updatedoptical pathway including aperture stops which correctly couple theelements is shown in FIG. 23.

Having the optical pathway defined, the elements can be arranged intheir folded configuration, which is a packaging for the optics thatprovides a compact footprint for full implementation in a consumerversion of the detector.

EXAMPLE II Optical Layout for Optic Bench Assembly

An embodiment of an optical layout for the optic bench assembly 40 isshown in FIGS. 24A. 24B, and 24C. To build the detector 4, Table 2provides specifications for commercially available components whichcould be used. The list is not exhaustive, but contains thespecifications relevant to calculating the expected performance of sucha detector and is provided primarily for this purpose. Two notableexceptions found in Table 2 are the AN LEDs with peak emissions below250 nm and the UVC reflecting DMD. Neither of these are commerciallyavailable at the time we are writing, however, each has beendemonstrated in the laboratory and can reasonably expected to becommercially available in the near future. Taniyasu, Y. et al., AnAluminum Nitride Light-Emitting Diode With a Wavelength of 210Nanometres, Nature, vol. 441, no. 7091, 2006; Fong, J. T. et al.,Advances in DMD-Based UV Application Reliability Below 320 nm, Proc.SPIE, vol. 7637, 2010; Thompson, J. et al., Digital Projection of UVLight for Direct Imaging Applications, DLP® Technology is Enabling theNext Generation of Maskless Lithography, 2008.

TABLE 2 Component Specifications LEDs: DMD:   Peak wavelengths 220, 230,. . . ,   Pattern rate ~10 kHz   320 nm   Width of active array ≥7 mm  Optic power output ≥1 mW each   Micromirror pitch 5.4 μm   Thermaloutput ~1 W   Overall efficiency at least 60%   FWHM 12 nm   Tilt 12°orthogonal to package   Rise-time <1 ms   Window material quartz glass  Packaging <10 mm Ø   Lifetime ≥2000 hours Spherical Grating:Photodiodes:   Focal length ~140 mm   Spectral response at least 200 nmto   Linear dispersion ~25 nm/mm   350 nm   Blaze λ 250 nm   Length ~6mm   Wavelength range 200 nm-350 nm   Rise time less than 5 μs  Efficiency at least 40% across entire   Photosensitivity ~0.11 A/W  range   Dark current less than 50 pA   Window material quartz glassFibers: Flowcell:   Core Ø 100 μm   Light-guided   Material fused silica  Length of flow 10 mm   NA 0.22   Overall length ~50 mm   NA .28Entrance Slit: Analog to Digital Converters:   Width 40 μm   SamplingRate ≥1 MHz   Height 2 mm   Bits ≥20

Calculations supporting expected specifications for the UVC LED detector4 together with a comparison to commercially available detectors of thetunable UV and photodiode array variety are provided immediately below.

Bandwidth

The minimal possible bandwidth for the detector 4 depicted in FIGS. 24A,24B and 24C is the entrance slit 12 width multiplied by the lineardispersion of the spherical grating 14, depending on concave gratingmagnification. For the entrance slit 12 of 40 μm and a linear dispersionof 25 nm/mm the minimal bandwidth is 1 nm. By tilting more columns (12)of the DMD 8 to the on position this bandwidth can be increased in stepsof 0.135 nm, which is set by the micro-mirror pitch of 5.4 μm.

Optical Throughput

The optical power incident on the sample photodiode can be calculated bymultiplying the cumulative irradiance of the LED sources, To, by thebandwidth, Δλ, and by the net efficiency of each optical element asshown in Equation 16 for n elements. The net efficiency is the productof the reflectance or transmission efficiency of an element η and thefill factor for an element F, which is the ratio of the numericalapertures squared.ϕ_(photodiode)=(I _(o)Δλ)Π_(t=1) ^(n) n _(i) F _(i)  (16)

Table 3 shows the approximate values of η and F for each element in thelight path. F is listed as 1 for all fill factors greater than unity.Total coupling efficiency from the LED to the fiber is assumed to be 20percent, which should be possible given use of a refractive-reflectivelens as mentioned herein, and is shown distributed between the fillfactor for the LED lens and the fiber.

TABLE 3 Reflection, Transmission, and Coupling Efficiencies of OpticsElement H F η_(net) LED lens 0.9 0.45 0.41 Fiber 0.95 0.45 0.43 EntranceSlit n/a 0.5 0.5 Grating 0.55 0.8 0.45 DMD 0.6 1 0.6 Mirror 0.9 1 0.9Sample Path BS 0.9 1 0.9 L1 0.98 1 0.98 LGFC 0.8 0.7 0.56 PD1 n/a 1 1Entire Sample Path 0.011 Reference Path BS 0.1 1 0.1 L2 0.98 1 0.98 PD2n/a 1 1 Entire Reference Path 0.002

By solving Equation 16 using the values given in Table 3, we can findthe flux incident on the sample and reference photodiodes 62, 64. Usingthe photosensitivity specification for the photodiodes we can then findthe signal and reference current. A summary of the outcome for severalcases can be found in Table 4 below.

TABLE 4 Sample and Reference Photodiode Responses for Various ScenariosSource I_(o) and Δλ (mW/ Φ_(r) Φ_(r) I_(s) I_(r) Bandwidth nm nm) mW mWmA mA Single LED, 1 nm 0.08 8.8 × 1.6 × 8.8 × 1.6 × 1 nm 10⁻⁴ 10⁻⁴ 10⁻⁵10⁻⁵ Single LED, 5 nm 0.08 4.4 × 8.0 × 4.4 × 8.0 × 5 mn 10⁻³ 10⁻⁴ 10⁻⁴10⁻⁵ Array, 1 nm 1 nm 0.11 1.2 × 2.2 × 1.2 × 2.2 × 10⁻³ 10⁻⁴ 10⁻⁴ 10⁻⁵Array, 5 nm 5 nm 0.11 6.1 × 1.1 × 6.1 × 1.1 × 10⁻³ 10⁻³ 10⁻⁴ 10⁻⁴

Signal to Noise Ratio

Using the currents from Table 4 and Equation 15 for the shot noisedominated signal to noise ratio, we can calculate the limiting SNRvalues for the same set of conditions. The result of these calculationscan be found in Table 5 immediately below.

TABLE 5 SNR and Noise Levels for Various Scenarios SNR Source andBandwidth 80 Hz Sampling Rate Noise Level Single LED, 1 nm 58,600 ±1.7 ×10⁻⁵ AU Single LED, 5 mn 131,000 ±7.6 × 10⁻⁶ AU Array of LEDs, 1 nm68,500 ±1.5 × 10⁻⁵ AU Array of LEDs, 5 nm 154,000 ±6.5 × 10⁻⁶ AU

Sampling Rate

The detector would use a sampling rate of 80 Hz to display thechromatographs, mimicking current methodology and keeping the shot noisedown. However, the electro-optical components in the detector arethemselves capable of operating at much higher frequencies. Asdemonstrated in Table 6 the DMD can be the limiting factor for thesystem.

TABLE 6 Max Operating Frequencies for Dynamic Elements Element RelevantSpec. Value Max Frequency LED Rise time <2 μs (dominated   1 MHz bydriving electronics) DMD Pattern rate 9.5 kHz 9.5 kHz Photodiode Risetime ~2 μs 0.5 MHz ADC Sample rate   1 MHz   1 MHz

If the DMD 8 is considered to timeshare among multiple wavelengths, itis apparent that 9.5 kHz will support continuous sampling of 118channels at 80 Hz. Since the instrument has a minimum bandwidth of 1 nmand a range of 110 nm, this feature can allow full sampling at everywavelength simultaneously, mimicking the functionality of a photodiodearray detector while maintaining the benefits of the referencingstrategy it shares with tunable UV detectors. Even at full sampling overthe entire range, the DMD 8 has seven percent excess capacity which canbe used for automatic wavelength and dark current calibrations in theloop while sampling.

After the capabilities of the DMD 8 have been fully utilized the rest ofthe components have at least 50 times the ˜10 kHz rate available. Thisexcess capacity can be used to sample each pattern created by the DMD 8multiple times and use averaging to filter out noise. Shot noiseincreases proportionally to the square root of the sampling rate, andaveraging decreases noise by the square root of the number of samples,so the shot noise will not be improved. However, other sources of noisepresent in the signal can effectively be filtered out by this method.

An electronic sampling rate of 1 MHz could accurately characterize theinstrument dynamics. Such information could be used to optimize machinespecific operation and troubleshoot, resulting in increased performanceand reliability for the end user.

Expected Resolution

In an embodiment, each column 22 of micro-mirrors on the DMD 8corresponds to a 0.135 nm step in the wavelength. The width of theentrance slit 12 prevents a bandwidth of this size, however. This stepsize in resolution is in fact the theoretical lower bound for theinstrument. In reality, several factors will increase this number to anempirically realizable resolution.

Resolution Sensitivity

In order to accurately estimate the resolution of the detector 4 we willhave to characterize its sensitivity to several variables: (1) distancebetween the entrance slit 12 and the spherical grating 14; (2) distancebetween the spherical grating 14 and the DMD 8; (3) width of theentrance slit 12; and (4) angular misalignment between the DMD 8 and thespectral plane of the grating 14. All of these can be determined tofirst order purely by the geometry of the light path.

If we take L_(α) to be the position of the entrance slit relative to thegrating then we can find the relation between changes in L_(α) andchanges in resolution as shown in Equation 17 where R is resolution anddl is the linear dispersion of the grating.

$\begin{matrix}{\frac{dR}{{dL}_{\alpha}} = {2{{dL}_{\alpha}}{NA}\; d_{l}}} & (17)\end{matrix}$

The same relation holds for the position of the DMD relative to thegrating, L_(H). We already know the relationship between the entranceslit width and the resolution and they are directly proportional to eachother where d_(l) is the constant. Finally, we can define therelationship between angular misalignments, dθ_(DMD), and resolution.Using the small angle approximation, we find the expression shown inEquation 18 where L_(DMD) is the length of the digital micro-mirrorarray.

$\begin{matrix}{\frac{dR}{d\;\theta_{DMD}} = {d\;{\theta_{DMD}\left( {L_{DMD}{NAd}_{l}} \right)}}} & (18)\end{matrix}$

Putting all of these together we can find an expression for thesensitivity of resolution to all of these factors, given in Equation 19.

$\begin{matrix}{\frac{\partial R}{{\partial L_{\alpha}}\;{\partial L_{H}}{\partial w_{slit}}\;{\partial\theta_{DMD}}} = {{2\mspace{11mu}{NA}\; d_{l}\mspace{11mu}\left( \left| {\partial L_{\alpha}} \middle| {+ \left| {\partial L_{H}} \right|} \right. \right)} + {{\partial w_{slit}}\; d_{l}} + {{\partial\theta_{DMD}}\;\left( {L_{DMD}\;{NAd}_{l}} \right)}}} & (19)\end{matrix}$

This expression for sensitivity can serve as a basis for error budgetingduring mechanical design to ensure that the actual resolution ofdetectors with this optics bench meet their target specifications.

Comparison to Existing UV Detectors for Liquid Chromatography

Table 7 provides a comparison of the specifications of the detector 4provided herein with several commercially available detectors.

TABLE 7 Comparison of UVC LED Detector Capabilities With Tunable UV andPhotodiode Array Detectors Specifications TUV PDA UVC LED WavelengthRange 190-700 nm 190-700 nm Variable within 210-320 nm Sampling Speed 80Hz 80 Hz Variable from 80 Hz-9.5 kHz Noise Level 2 × 10⁻⁶ to 6 × 10⁻⁶ 3× 10⁻⁶ 6.5 × 10⁻⁶ (shot noise, no filter) Bandwidth 5 to 6.5 nm 1.2 nmto 4 nm Variable from 1-110 nm Resolution/Accuracy ±1 nm ±1 nm ±0.2 nmIrradiance of source 0.1 μW nm⁻¹ cm⁻² 0.1 μW nm⁻¹ cm⁻² Variable up to1.5 μW nm⁻¹ cm⁻² Self-referencing Yes No Yes Self-Calibration 5 min. atwarmup 5 min. at warmup 0.05 s (any time) Start-up time 20 min. 20 min.<1 min.AlN based LEDs have many advantages over traditional UV light sourcessuch as increased lifetime, higher intensity per unit bandwidth, lowheat generation, and can be rapidly modulated. The DMD 8 permits timesharing over multiple wavelengths, variable bandwidth and the potentialfor multiple types of auto-calibration.

EXAMPLE III Prophetic Optical Detector

In an embodiment, the detector 4 includes a plurality of LEDs (alsoreferred to sometimes as a “bank”) as the light source 50. The LED hasan aluminum nitride (AlN) substrate to emit light in a low UV range inwavelengths comparable to that of the deuterium UV lamp. To cover abroader range of wavelength, the detector 4 can have up to multiple LED6 (i.e., up to a dozen) to generate any combination of peak wavelengthsbetween 210 nm and 320 nm. Both presence and concentration of aparticular substance (referred to herein as a “constituent” or“compound”) in a sample can be determined by recording the amount of UVradiation absorbed at one or more particular wavelengths. Light from theLED 6 and an onboard mercury arc calibration lamp (not shown) can betransmitted to the entrance slit 12 using fused silica fiber optics (notshown).

In an embodiment, the entrance slit 12 has a single aperture, 1 mm longand 40 microns wide, to project light onto a spherical holographicgrating. The grating will diffract the light according to its wavelengthand will focus a light beam 58 onto a Digital Micro-mirror Device(“DMD”) 8. The DMD 8 can select a single wavelength or a range ofwavelengths and reflect the light beam 58 towards a spherical mirror 56.Wavelengths not selected can be directed onto a light dump 54. The lightincident on the spherical mirror 56 can be reflected toward the beamsplitter 60, which, in turn, will direct a small portion of the lighttoward reference photodiode 62. Remaining light will be directed to themain photodiode 64 through the flow cell 66. The reference photodiode 62can enhance the signal to noise ratio (“SNR”) of the processed data bydirectly cancelling out different forms of noise. The detector 4 can beversatile, with similar (or improved) capabilities as the TUV or thePDA. Proposed specifications of the UV-LED detector are shown in Table 8immediately below:

TABLE 8 Specifications of UV-LED Detector Specifications UV-LED DETECTORWavelength Range Variable within 210-320 nm Sampling Speed Variable from80 Hz-9.5 kHz Noise Level 6.5 × 10⁻⁶ (shot noise, no filter) BandwidthVariable from 1-110 nm Resolution/Accuracy ±0.2 nm Irradiance of sourceVariable up to 1.5 μW nm⁻¹ cm⁻² Self-referencing Yes Self-Calibration0.05 s any time during run Start-up time <1 min

EXAMPLE IV Design Considerations for an Optics Bench Assembly MaterialSelection

Attributes of a specific material for the optics bench assembly 40 caninclude a set of physical, mechanical and chemical properties thatcharacterizes the material as required for an intended service. TheAshby Material Selection method of material selection has four steps:(1) translation of design requirements to quantitative and qualitativeterms such as function, constraints, objectives and free variables; (2)initial screening of materials based on derived attribute limits fromconstraints; (3) ranking the screened material based on material index,which is a criterion of excellence that maximizes or minimizes theobjective; and (4) final screening of materials based on supportinginformation such as availability, cost, behavior in working environmentsfor top ranked material. See, Ashby, M. F., Materials Selection inMechanical Design, Third Edition, 3rd ed. 2005.

Translation

Any engineering component has a multitude of functions such as;supporting a load, conducting heat, containing pressure, etc. Thesefunctions can be achieved while subjected to certain constraints laiddown by the design such as maximum dimensions, thickness, maximum loadcapacity, etc. During the design process, the designer is looking toachieve his or her design objectives (such as making the part lighter orcheaper) and to achieve these objectives, he or she is free tomanipulate the variables which are not constrained by designrequirements. These are called the free variables. Therefore, the firststep of material selection is to reinterpret the design requirements interms of the function, constraint, objectives and free variables.

Screening

Initial screening eliminates the materials which do not meet the basicrequirements set by the constraints. These constraints are known as theattribute limits. Screening is done with the help of material selectioncharts which plot a combination of properties of interest, (for instanceYoung's modulus versus density or strength versus density) and bymapping out the fields in property-space occupied by each materialclass, and the sub-fields occupied by individual materials. Attributelimits are plotted on material selection charts as horizontal orvertical lines. The material lying in the optimal region defined by theattribute limits matches the design requirements and has potential to beused in the final product/design.

Ranking

In order to rank the screened candidates, optimization criteria known asMaterial Indices is derived which measures how well a material matchesthe design requirements. It is a property or a group of properties thatdefines performance and therefore maximizing material index willmaximize the performance for a given design.

Supporting Information

After ranking and short listing the top candidates which satisfies alldesign constraints and meets the objective requirements, other detailsare necessary for selecting the final best materials for the design. Thedetails required are corrosion behavior in a particular environment,information on availability and pricing, aspects of past history of thematerial and established uses, in-house expertise or availability ofmachine tools for manufacturing, etc.

Manufacturing Process Selection

Similar to the material selection process, the manufacturing process isselected by translating the design requirements into function,constraints, objectives and free variables. Function defines what thefinal finished product is intended to do. Constraints can be set basedon design requirements such as material, shape, mass, section thickness,tolerance requirements and annual production volume. Objectives definewhich parameter of the manufacturing process (cost, quality, time, etc.)needs to be maximized or minimized. Free variables are usually thechoice of manufacturing process or chain of manufacturing processes thatcan meet the objectives while also satisfying the constraints. Whileperforming the initial screening, processes which do not meet the basicdesign requirements are eliminated. Selection charts such asprocess-material matrix, process-shape matrix, property bar chart areused to select the appropriate manufacturing process. Additionalinformation such as accessibility and infrastructure availability for aparticular manufacturing process are also considered while selecting thebest suited manufacturing process.

EXAMPLE V Optics Bench Assembly Construction and Serviceability

In the optics bench assembly 40, parts required for proper functioningof the product can include parts that are easy to align and assemble.Components can be such, that there is little or no resistance toinsertion. Chamfers can be provided to guide the insertion of two matingparts. Preferably, clearance can be generously provided and care takento avoid clearances that will result in a tendency for parts to jam orhang-up during insertion. Common parts, processes, and methods can bestandardized across all models and even across product lines to permitthe use of higher volume processes that normally result in lower productcost. A part can be designed such that it is located before beingreleased.

A potential source of problem arises when a part is released at theplace of its assembly before it is positively located. Under thesecircumstances, reliance is placed on the trajectory of the part beingsufficiently repeatable to locate it consistently. Wherever possible,the necessity of holding parts down during manipulation of thesubassembly or during the placement of another part should be avoided.For manual assembly, both access and vision is preferably notrestricted. For automated assembly, insertion in a straight line fromabove is preferred.

To avoid, problems and issues related to manufacturability, reliability,serviceability in the optics bench assembly 40, consideration of issuesor problems with earlier models can prevent repeating the same mistakes.Anderson, D. M., Design for Manufacturability: How to Use ConcurrentEngineering to Rapidly Develop Low-Cost, High-Quality Products for LeanProduction, CRC Press, 2014. The assembly sequence can be concurrentlyengineered while designing the product. Designing for easy partsfabrication, material processing, and product assembly is a primarydesign consideration. Even if labor cost is reported to be a smallpercentage of the selling price, problems in fabrication, processing,and assembly can generate enormous overhead costs, cause productiondelays, and demand the time of precious resources.

Over-constraining an assembly leads to high tolerance demands. It alsoinduces stress in the assembly. Over-constraints are also costly,causing quality problems and compromising functionality because thedesign will work only if parts are manufactured with extremely tighttolerances. On the other hand, under-constraining can have one or moreunfixed degrees of freedom and thus results in loosely assembled parts.Avoidance of over-constraining or under-containing the assembly isrecommended. Whitney, D. E., Mechanical Assemblies: Their Design,Manufacture, and Role in Product Development, Volume 1, OxfordUniversity Press, 2004.

Components and assembly parts of the optics bench assembly 40 can bedesigned such that there is an unobstructed path for entry into thisdevice, preventing damage to the component, part or optics benchassembly 40. Also, there can be unobstructed access for tools and thetool operator, whether that is a worker or robot arm, for assembly andrepair. Awkward contortions in assembling a product manually can lead toworker fatigue, slow throughput, poor product quality, and even workerinjury. Anderson, D. M., Design for Manufacturability: How to UseConcurrent Engineering to Rapidly Develop Low-Cost, High-QualityProducts for Lean Production, CRC Press, 2014. Preferably, individualcomponents and/or sub-assemblies are independently replaceable, givingthe advantage of easily replacing parts without having to remove otherparts first. The order of assembly can then be more flexible becauseparts can be added in any order. Another advantage of independentlyreplaceable parts is the ease of adding options later, either in thefactory or in the field. In terms of supply chain, this helps to copewith part shortages, allowing the rest of the product to be built andwhen components or parts are not available.

Having considerations toward sequence of assembly, the component withlowest mean time to failure is preferably assembled at the end(particularly for assemblies for which the components are notindependently replaceable) and the easiest to remove from the assemblyso that it can be easily replaced without much hassle. In an embodiment,future upgrades and other part options can be easily assembled into theproduct without a complete redesign. This increases overall product lifeby adding future upgrades and helps generates more profit even in latestages of the product lifecycle. Considerations towards future upgradesinclude allowing space for added parts, mounting holes, part access,tool access, software reconfiguration, extra utility capacity, etc.

The product architecture can be structured into modules andsub-assemblies, as appropriate. Sub-assemblies can be built inspecialized departments and tested separately from the overall product.This streamlines the manufacturing and assembly process. Alsosub-assemblies simplify product testing, as individual sub-assembliescan be pre-tested and/or do not require extensive re-testing duringfinal assembly. It is also easier to identify failure modes and qualityproblems in a product with subassemblies. Then, diagnostic attention canbe focused to the sub-assemblies with highest likely probability offailures. Sub-assemblies can also improve serviceability as thedefective subassembly or parts can be easily repaired or replaced withnew ones. A modular design allows for replacement of obsolete moduleswith upgraded ones, increasing the product life and performance.

Finally, assembly using liquid adhesives and sealants should be avoided.Long drying times with adhesives and sealants can compromise flowmanufacturing. Instead, alternatives such as screws or nuts coated withretention compound, fasteners with deformed threads, lock washers,compliant gaskets or even effective design strategy such optimalenclosures and built-in seals can be considered.

Thermal Management

Thermal distortion of components due to thermal gradients or due tochange in temperature over time, is a common cause of non-repeatabilityand dimensional instability in components. This negatively affects thefunctionality of the product due to thermally induced errors. Some ofthe guidelines to increase the thermal stability are immediatelydiscussed below. Hale, L. C., Principles and Techniques for DesigningPrecision Machines, MIT, 1999.

Sensitivity Reduction

Components of the optics bench assembly 40 can be assembled in such away that symmetric temperature distributions are achieved in symmetricstructures which in turn reduces thermal distortions. Materials with alow coefficient of thermal expansion can be used to reduce variations ingeometry due to variations in temperature. Components with the mostcritical temperature sensitivity can be located near the air inlet toprovide the coolest air flow.

Management of Heat Sources

Sources of heat are placed outside the controlled environment andunnecessary heat sources can be eliminated where possible. Hot spots canbe avoided by spot cooling using a small fan. Components that dissipateless heat are preferred over high heat dissipating components. Sourcesof heat can be isolated from other sensitive components and the flow ofheat removing fluids over other sensitive parts of the system can beprevented. The isolation of components with high heat dissipation can beachieved by placing those components near the enclosure air exits. Heatsources with the controlled environment can remain constant and theamount of heat dissipation cannot vary over time.

Control of the Machine Environment

The room/lab air temperature can be controlled to reduce temperaturevariations in the optics bench assembly. Heat leakage into or out of theroom/lab can be prevented to reduce variations in the room airtemperature. The structure of the optics bench assembly 40 can beisolated and the temperature of the metrology loop can be controlled. Atemperature controlled fluid flowing over the subassembly/component canbe used to regulate its temperature. The effect of viscous heating inhigh speed fluid flows can also be considered. Indeed, the human bodyrepresents a heat source of about 100 watts. Thus use of insulatingclothing such as gloves for precision applications is recommended. Dustcan be kept out of the optics bench assembly 40 enclosure bypressurizing it or blowing air. The largest possible filter can be usedin order to increase dust capacity and reduce pressure drop. Temperaturecontrol is the most reliable, effective and least expensive means toreduce thermal errors. The design challenge is how to provide sufficientcontrol for minimal cost.

Shock Isolation

Mechanical shock is a sudden and severe non-periodic disturbance of amechanical system which causes significant forces that may damage thesystem. Shock loads when applied to a portion or entire optics benchassembly 40 may result in elastic or inelastic deformation of opticalenclosure, impairment of optical alignment, and/or failure of fragileoptical components. Such conditions are usually encountered duringshipping, when for example the transportation truck encounters potholeor bump, or when someone accidentally drops the optics bench assembly 40while moving it. Some of the major causes of shock in a system include:(1) sudden change in the level of energy in the system by suddenintroduction of energy; (2) application of a sudden force; and (3)abrupt change in motion, velocity or acceleration of the system Theshort duration transient loads called the shock pulse have complex waveshapes. To simplify the analysis the complex wave shapes can beapproximated to a nearest simple wave shape with a known response. Theinput shock pulses are characterized by maximum amplitude, time durationand approximate shape.

The majority of shock pulses encountered by objects can be categorizedas half sine shock pulse, versed-sine shock pulse, rectangular shockpulse, triangular shock pulse, drop/freefall shock, velocity shock,acceleration impulse and force impulse. Shock resistance is defined byits fragility, which in turn is expressed as the highest level ofacceleration beyond which the equipment will fail to operate withinspecification. Shock mounts are used to absorb the input accelerationand release the shock energy over a broader time base, thus reducing theoutput acceleration. The shock mount shall not permit the outputacceleration to exceed the fragility level of the most delicatecomponent in an assembly. The optics bench assembly 40 specificationsgenerally define fragility in terms of acceleration in multiples ofgravity. The shock level associated with normal manual handling of theoptical instruments is around 3Gs. Yoder, P., Opto-Mechanical SystemsDesign, Fourth Edition, Volume 1: Design and Analysis of Opto-MechanicalAssemblies, Volume 1, CRC Press, 2015.

Vibration Isolation

Every structure has the tendency to vibrate at certain frequencies,which are known as natural or resonant frequencies. The naturalfrequency of a piece of equipment is given by Equation 1, where k is thestiffness and m is the mass of the equipment.

$\begin{matrix}{f_{n} = {\frac{1}{2\pi}\mspace{11mu}\sqrt{\frac{k}{m}}}} & (20)\end{matrix}$

Each natural frequency is associated with a certain shape, called modeshape, which the model tends to assume when vibrating at that frequency.Resonance is a condition in which a structure or component is excited bya dynamic load at one of its natural frequencies leading to largedisplacements and stresses in the component. For un-damped systems,resonance theoretically causes infinite motion. Damping, however, puts alimit on the response of the structures due to resonant loads.

The efficiency of flow of vibrational energy is quantified bytransmissibility, which is defined as the ratio of dynamic output todynamic input. In other words, transmissibility quantifies howefficiently a forcing vibration can produce an excited vibration.Vibration isolation is attained by maintaining a proper relationshipbetween the disturbing frequency and the system's natural frequency.Transmissibility measures the effectiveness of isolators in reducingvibration.

FIG. 25 shows transmissibility plotted against the ratio of disturbingfrequency and the natural frequency of a system. In FIG. 25, the plotshows the disturbing frequency is low compared to the natural frequencyof the system the transmissibility is close to 1. When the disturbingfrequency approaches the natural frequency, transmissibility is high.This implies that the output is higher than the input. When the ratio ofthe disturbing frequency and natural frequency is greater than √2,transmissibility is less than 1 and the system is isolated because theoutput is lower than the input. Elastomeric springs are commonly usedfor vibration isolation. Most of the vibration isolators also possessdamping but in varying degrees. Without damping a system would continueto vibrate at its resonant frequency for an extended period of time evenif the excitation load is removed. With damping, the oscillations decayquickly as some of the excitation energy is converted into heat. Thegreater the amount of damping, lower is the transmissibility atresonance. Damping is advantageous when the system operates at or nearthe natural frequency as it reduces the peak response at resonance.

Design for Serviceability

As shown in FIG. 26, the optics bench assembly 40 can be designed sothat the individual sub-assemblies are independently replaceable. Thereare multiple advantages with independent replaceable components andsub-assemblies. First, it allows sub-assemblies such as the gratingassembly and mirror assembly to be calibrated and tested independentlybefore being assembled to the optics bench. Second, serviceability ofthe optics bench assembly 40 is improved such that a nonfunctional partin the assembly can be removed for repairs or it can be replaced with anew part without removing any other components first. Third, componentsand parts can be added in any order without any specific assemblysequence. Another advantage of using independently replaceablesub-assemblies is that any compatible future upgrade of the individualparts can be seamlessly integrated with the current system, increasingthe product lifecycle of the detector. Finally, the optics benchassembly 40 can be used for other detectors having a similar opticallayout but different component part specifications.

EXAMPLE VI The Optics Bench Assembly

As described herein, the optics bench assembly 40 comprises both opticalcomponents and structural components, together referred to sometimes asoptics bench assembly 40 components or components. Optical components ofthe optics bench assembly 40 can include: (1) a light entrance slit 12;(2) a spherical grating 14; (3) a digital micro-mirror device (DMD) 8;(4) a spherical convex mirror 56; (5) a beam splitter 60; (6) areference photodiode 62; (7) a main photodiode 64; and (8) a flow cell66. Structural components of the optics bench assembly 40 describedherein include: (1) a light dump 54 (sometimes referred to herein as a“light dump/shield” or a “light shield”); (2) an optics bench assemblycasing 44; (3) an optics bench assembly cover 70; (4) a mirror, (5) agrating mounting mechanism 71; (6) a plurality of mounting brackets 72;and (7) a plurality of fasteners 73.

In the optics bench assembly 40, optical components can be located toeliminate relative motion between any two components mounted on thebench. Each component is compatible with light of wavelength rangingfrom 150 nm to 1000 nm (UV to IR). The optics bench assembly 40 caninclude the light dump 54 to absorb or otherwise suppressing any straylight or act as a light beam dump. Further, in an embodiment describedherein, each of the optical components are isolated from vibrations,shock, external heat sources, environmental temperature variation, dustand airborne contaminants, humidity, and corrosion due to solvents andchemicals, and abrasion/erosion. In an embodiment of the optics benchassembly 40, heat that is generated in the components can be conductedaway. As described herein, the optics bench assembly 40 can bemanufactured and assembled to allow for ease of calibration andserviceability. In an embodiment, an effective service life cycle can beover 15 years.

In an embodiment, the geometric shape of the optics bench assembly 40 isdetermined by the relative position and spatial arrangement of theoptical components, which are determined via an optical layout of theUV-LED detector. FIG. 27 depicts an embodiment of an optical layout forthe UV-LED detector. Besides the spatial arrangement of the opticalcomponents, manufacturability, assembly and serviceability are otherfactors that can determine the layout of the optics bench assembly 40.In addition, the overall height of the optics bench assembly 40 can belimited by the height of the detector 4 or detector module.

As shown in FIG. 28, the optics bench casing 44 is a rigid enclosureholding the optical elements together. The light dump 54 (that canabsorb any stray light from light slit), the DMD 8 and the grating canalso be part of the optics bench casing 44. Another feature is equallyspaced mounting feet, or mounting brackets 72 in an optics bench casing44. The mounting feet 72 attach the optics bench assembly 40 to thedetector frame 74 and act as mounting points for shock and vibrationisolators. The side walls 75 of the optics bench assembly 40 have one ormore slots through which the optical components enter into the opticsbench casing 44. The slots are sufficiently bigger than the maximumdimensions of the optical components to provide easy accessibility andto prevent any damage to optical components during assembly.

The optics bench assembly 40 can be structured into sub-assemblies. Thesub-assemblies include spherical mirror assembly 56, grating 14, DMD 8,beam splitter 60 and reference photodiode 62, and flow cell 66. Divisioninto subassemblies allows for individual calibration and testing of themirror 56 and grating 14 before being assembled into the optics benchassembly 40. Subassemblies allow parts to be built in specializeddepartments or outsourced to a supplier with cheaper cost or betterquality, without affecting other parts in the optics bench assembly 40.The selection of a suitable joining method of the subassemblies to theoptics bench casing 44 is equally important. Permanent joining methodsare inappropriate because some of the optical components such as DMD 8and spherical grating 14 have smaller mean time to failure than othercomponents and will need to be replaced after much shorter theirintended service lives.

Therefore, a method of joining allows for assembly and disassembly ofall the components. On the other hand, certain components can be rigidlyheld in place during operation and cannot be loosen due to slightvibrations. The relative positioning and orientation of opticalcomponents, for example, in an optical instrument or the detector iscritical. Optical components can also be individually mounted andaligned in a precise fashion on the optics bench. Given all the aboveconstraints, threaded fastener are preferred for assembly.

As shown in FIG. 29, each optical component can be located using twoaccurately machined locating pins 76 and held in place on the opticsbench 42 with two fasteners. The components can be directly bolted tothe optics bench casing 44 which has been precision machined. Thelocating pins 76 can be press-fit in machined holes on the optics benchassembly 40. Pins help to align and orient a component or part duringassembly. Pins (not shown) can also reduce the number of fasteners 73required for assembly and shortens the overall assembly time. Opticalcomponents can be assembled manually to the optics bench 42 and partsdesigned so that access and vision of the assembler is not restricted byany other part. The fasteners 73 can be standardized in all thesub-assemblies for metric M4 size bolts except in the top cover.Standardizing fasteners 73 help in economies of scale and alsosimplifies the assembly process. Slots in the optics bench casing havesufficient clearance to allow an unobstructed assembly path and toprevent damage to the optical components during assembly.

Finally, the optics bench assembly 40 can be made of materials that canhave: (1) a low coefficient of thermal expansion to maintain dimensionalstability; (2) a high thermal conductivity to minimize distortion due tothermal gradient; (3) a high stiffness to minimize vibrationsensitivity; and (4) a high strength and toughness to minimizedeformation during impact loading Thermal expansion can be compensatedby having an effective and robust thermal management system thatmaintains the average temperature of the optics bench assembly 40 withinacceptable limits. Thermal gradients cause distortion of components andparts for which compensation is not possible. Therefore, during materialselection, minimizing thermal gradients can be given priority. Inaddition, vibration causes natural excitation which induces noise intothe LC system 2 due to which the functionality of the detector 4 can beseverely affected. Material cost and easy availability are alsoimportant considerations while selecting the final suitable material.The Ashby methodology of material selection is used to find the bestsuited material for the optics bench.

TABLE 9 Translation Chart for Material Selection FUNCTION Support andprotect optical components CONSTAINTS Optics bench shape and dimensionsOBJECTIVE Maximize thermal conductivity, minimize vibration sensitivity,minimize deformation during impact loading FREE VARIABLES Material

The optics bench assembly 40 can be made of material that can easilyremove the heat generated in internal components during operation toprevent build-up of high temperatures inside the optics bench 42. Thiscan be achieved by having a material that has high value of coefficientof thermal conductivity. As the first screening step, materials withcoefficient of thermal conductivity smaller than 10 W/mK are eliminated.As shown in FIG. 30, only metals and majority of ceramics qualify assuitable materials after the first screening step. the performance indexis found out by considering a simple case of one dimensional heat flowthrough the walls of the optics bench. The steady state Fourier law isgiven by Equation 21, where

$\begin{matrix}{q = {{- \lambda}\mspace{11mu}\frac{dT}{dx}}} & (21)\end{matrix}$

Material Index for Minimizing Thermal Gradient

The performance index is obtained by one dimensional heat flow throughthe walls of the optics bench. The steady state Fourier law is given byEquation 22, where q is the heat flux, λ is coefficient of thermalconductivity of the material and

$\frac{dT}{dx}$is temperature gradient.

$\begin{matrix}{q = {{- \lambda}\frac{dT}{dx}}} & (22)\end{matrix}$The strain developed due to temperature gradient is given by Equation23, where α is coefficient of linear expansion of the material and ΔT isthe difference in temperature of the optics bench casing and the ambienttemperature.

$\begin{matrix}{\epsilon = {{\alpha\Delta}\; T}} & (23) \\{\frac{d\;\epsilon}{dx} = {\alpha\frac{dT}{dx}}} & (24)\end{matrix}$Equation 25 is derived by combining Equations 23 and 24, where

$\frac{d\;\epsilon}{dx}$is the measure of distortion due to thermal gradient.

$\begin{matrix}{\frac{d\;\epsilon}{dx} = {q\left( \frac{\alpha}{\lambda} \right)}} & (25)\end{matrix}$Now the thermal gradient can be minimized by minimizing the value of

$\frac{\alpha}{\lambda}$or selecting materials with large values of index M₁, which is given byEquation 26.

$\begin{matrix}{M_{1} = \frac{\lambda}{\alpha}} & (26)\end{matrix}$

To have good dimensional stability and minimize distortion due tothermal gradient, the material should have low coefficient of thermalexpansion and high coefficient of thermal conductivity. FIG. 31 showsthat the value of the index

$M_{1} = \frac{\lambda}{\alpha}$increases by moving towards the bottom right side of the chart. Theattribute limits are set at λ=10 W/mK and

$M_{1} = {10^{7}\frac{\mu\mspace{14mu}{stain}\text{/}K}{W\text{/}{mK}}}$to eliminate materials with low thermal conductivity and high thermalexpansion. Metals such as aluminum, copper, tungsten alloys, silicon andtechnical ceramics such as tungsten carbide, silicon carbide, aluminumnitride satisfy the above criteria.

Material Index for Minimizing Vibration Sensitivity

The sensitivity to the external excitation is minimized by maximizingthe natural frequencies of the component. For the sake of simplicity,the optics bench is assumed to be resting on two mounting supports andexcitation force acting through its center of gravity. This isequivalent to a light and stiff square beam of side b, subjected tothree point bending load. Stiffness of the beam in the above conditionis given by Equation 27, where F is the force acting on the beam, δ isthe deflection of the beam, E is the Young's modulus of the beam'smaterial, L is the length of the beam, I is the second moment of areagiven by

${\frac{b^{4}}{12}\mspace{14mu}{or}\mspace{14mu}\frac{A^{2}}{12}},$A is the cross-sectional area of the beam and C is a constant whosevalue depends on the type of the loading.

$\begin{matrix}{S = {\frac{F}{\delta} = \frac{CEI}{L^{3}}}} & (27)\end{matrix}$Mass of the beam is given by Equation 28, where ρ is the density of thebeam's material.m=ρAL  (28)Combining equation for stiffness and second moment of inertia with themass equation we get Equation 29.

$\begin{matrix}{m = {\left( \frac{12S}{C} \right)^{1\text{/}2}(L)^{5/2}\left( \frac{\rho}{E^{1\text{/}2}} \right)}} & (29)\end{matrix}$The flexural vibrations have lowest frequencies and they areproportional to

$\frac{E^{1/2}}{\rho}{◯.}$Ashby, M. F. Materials Selection in Mechanical Design Third Edition, 3rded. 2005. Thus the sensitivity to vibration can be minimized byselecting a material with large value of the index M₂ given by Equation30.

$\begin{matrix}{M_{2} = \frac{E^{1/2}}{\rho}} & (30)\end{matrix}$

As shown in FIG. 32, value of the index M₂ increases by moving towardsthe top left corner of the chart. The attribute limits are set at E=1GPa and

$M_{2} = {1\frac{{GPa}^{1/2}}{{Mg}\text{/}m^{3}}}$to eliminate materials of low stiffness. Some of the qualifyingmaterials according to the above criterion are ceramics, majority of themetals, composites and some natural materials such as wood.

Material Index for Minimizing Deformation During Impact Loads

During impact loading, it is assumed that the optics bench of mass mfalls from a height h under the influence of gravity. After contact withthe floor the optics bench deforms due to stresses developed. The amountof deformation depends on the stiffness of the component. The change inpotential energy U after the impact is given by Equation 31.U=mgh  (31)This energy is absorbed by the material through the deformation of thecomponent. This is known as strain energy and is given by Equation 32,where σ is the stress developed due to impact loading, ϵ is the straindeveloped in the material, V is the volume of the part.Strain Energy∝σϵV  (32)The Hooke's law relation is given by Equation 33.

$\begin{matrix}{E = \frac{\sigma}{\epsilon}} & (33)\end{matrix}$Substituting Equation 33 into Equation 32, gives the elastic strainenergy per unit volume, the expression for which is given by Equation34.

$\begin{matrix}{{{Elastic}\mspace{14mu}{Strain}\mspace{14mu}{Energy}\mspace{14mu}{stored}\mspace{14mu}{per}\mspace{14mu}{unit}\mspace{14mu}{volume}} \propto {\frac{1}{E}\sigma^{2}}} & (34)\end{matrix}$

The optics bench will be permanently deformed if the stress σ developedafter impact loading exceeds the failure strength σ_(f) of the material.Therefore to prevent deformation, the stress developed in the part afterimpact loading can be less than the failure strength of the material.This constraint is shown by Equation 35.σ≤σ_(f)  (35)The maximum strain energy that can be stored in the body withoutpermanent deformation is known as proof resilience U_(m), which is givenby Equation 36. Therefore the objective is to maximize the maximumenergy density or proof resilience of the body.

$\begin{matrix}{U_{m} \propto \frac{\sigma_{f}^{2}}{E}} & (36)\end{matrix}$Thus the deformation after impact loading can be minimized, by selectinga material with large value of the index M₃, given by Equation 37.

$\begin{matrix}{M_{3} = \frac{\sigma_{f}^{2}}{E}} & (37)\end{matrix}$

As shown in FIG. 33, value of the index M₃ increases by moving towardsthe right of the chart. The attribute limits are set at E=1 GPa and

$M_{3} = {100\frac{{MPa}^{2}}{GPa}}$to eliminate materials with low value of Young's modulus and lowstrength. Some of the qualifying materials according to these criteriaare ceramics such as Tungsten carbide, Silicon Carbide, most of themetals, composites and some of the polymers such as PMMA, PC,Polyurethane, and Polyamide.

Material Properties Comparison

The material properties are shown in the Table 10 for comparison. Thevalues of the material indices M1, M2 and M3 as shown in Table 4, arederived from Table 10.

TABLE 10 Mechanical Properties of Top Ranked and Common Materials YieldThermal Thermal Strength Conductivity Expansion Density MATERIAL E (GPa)(MPa) (W/mK) (10⁻⁶/K) (10³ kg/m³) Silicon 350 3125 155 4 3.1 CarbideAluminum 320 2335 140 5 3.29 Nitride Aluminum 72.4 170 151 21.4 2.67Copper 130 265 275 17 8.93 Zinc 80 265 117 25 6 Steel 200 750 15 16 7.8PEEK 4 80 0.25 133 1.31 Bulk 9.5 28 13 30 1.89 Molding Compound (BMC)940 [11]

TABLE 11 Material Indices of Top Ranked and Common Materials MATERIAL$\quad\begin{matrix}{M_{1} = \frac{\lambda}{\alpha}} \\\left( \frac{W\text{/}{mK}}{10^{- 6}\text{/}K} \right)\end{matrix}$ $\quad\begin{matrix}{M_{1} = \frac{E^{1/2}}{\rho}} \\\frac{({MPa})^{1/2}}{{Mg}\text{/}m^{3}}\end{matrix}$ $\quad\begin{matrix}{M_{3} = \frac{\sigma_{f}^{2}}{E}} \\\frac{({MPa})^{2}}{GPa}\end{matrix}$ Silicon 38.75 6.0 27902 Carbide Aluminum 28.00 5.4 17038Nitride Aluminum 6.95 3.2 936 Copper 16.17 1.3 540 Zinc 4.68 1.5 878Steel 0.94 1.8 2813 PEEK 0.002 1.5 1600 Bulk Molding 0.43 1.6 83Compound (BMC) 940 [11]As shown in Table 10 and Table 11, silicon carbide has the best overallproperties for the optics bench application followed by aluminum nitrideand aluminum. Polymers do not qualify mainly due to the poor ratio ofthermal conductivity to thermal expansion, which will lead to distortionand dimensional instability at high operating temperatures.

Supporting Information for Material Selection UV Compatibility

Since the detector uses UV-LEDs as the light source, one of the basicrequirements of the materials used for the optics bench 42 is to be UVcompatible and resist photo degradation under long UV exposure. This isalso necessary in order to have a long lifecycle of the optics benchsince materials that are not UV stable will degrade over time and becomebrittle, crack, decolorize, warp, etc. UV compatibility can bedrastically improved by coating the base material with other materialswhich prevent UV degradation and also absorb/suppress any stray orscattered UV radiation. Ceramics and Metals are much less susceptible toUV based damage as compared to polymers. Therefore ceramics such as SiCor AlN and metals such as aluminum are better suited materials for theoptics bench than polymers.

Material Cost

FIG. 34 shows the cost per unit weight of different material class. Anapproximate cost comparison (cost per unit weight) between aluminum andceramics (SiC and AlN) shows that ceramics costs at least 5 times thanthat of aluminum alloys. This cost difference outweighs the advantagesin properties that ceramics have over aluminum. Thus using ceramics as amaterial for optics bench is not practical due to its prohibitively highcost.

Availability

Aluminum and its alloys are more readily available and more widely usedas compared to ceramics. The manufacturing infrastructure for aluminumis also well established and readily accessible and compared to ceramicsaluminum processing is cheaper.

Selection of Aluminum Alloy

The analysis that aluminum is a suited material for the optics benchtakes into consideration a lot of factors such as strength, dimensionalstability, vibration sensitivity and cost. Aluminum alloys have muchbetter properties for opto-mechanical applications than pure form ofaluminum. Some of the commonly used aluminum alloys are Alloy 1100,Alloy 2024, Alloy 6061, Alloy 7075 and Alloy 356. Out of these, Alloy356 is the best suited alloy for general purpose optical instruments.The main alloying composition for aluminum 356 is 7% Silicon and 0.3%magnesium. The higher purity variant of the alloy (in terms of chemicalcomposition) is designated with an A before the number 356. Some of theproperties of aluminum A356 are good castability by sand, permanent moldand die casting methods making it an excellent candidate for intricateand complex castings including: good machinability characteristics;moderate to high strength; excellent corrosion resistance and goodweldability characteristics. The common mechanical properties ofaluminum A356 is shown in the Table 12 immediately below.

TABLE 12 Mechanical Properties of Aluminum Alloy A356 Young's YieldThermal Thermal Modulus Strength Conductivity Expansion Density Material(GPa) (MPa) (W/mK) (10⁻⁶/K) (10³ kg/m³) Al A356 72.4 >165 151 21.4 2.67

EXAMPLE VII Engineering Analysis of the Optics Bench Assembly

A drop test analysis on 3D CAD software simulation can be carried out totest if the optics bench 42 (as used in an optics bench assembly 40described herein) can maintain its structural integrity when it issubjected to impact loads. As shown in FIG. 35, this test can be carriedout under the assumption that the optics bench 42 will fall freely onthe base from height of 1000 mm on a rigid ground under the influence ofacceleration due to gravity. The testing specification is in accordancewith the “Optics and Photonics-Environmental test methods—ISO 9022”(Appendix A, Method 33 Freefall test); Yoder, P., Opto-MechanicalSystems Design, Fourth Edition, Volume 1: Design and Analysis ofOpto-Mechanical Assemblies, Vol. 1, CRC Press, 2015.

The amount of stress developed in an optics bench casing 44 due to theimpact loading can be analyzed and compared with the yield strength ofaluminum A356. The optics bench 42 should be designed such that it notonly maintains its shape and form after the impact but it can protectthe parts of the assembly mounted within it. To simplify the meshing andanalysis, the optical components are modeled as cuboid having the samemass as that of original parts.

In an embodiment, the optics bench 42 was tested for impact loadinghaving a wall thickness of 4 mm. The results of the drop test on theoptics bench 42 having a 4 mm wall thickness is shown in FIG. 36. Theresults indicate that the maximum stress value is 233.6 MPa. This valueis much greater than the yield strength of an aluminum wall (A 356)which is around 170 MPa. The results show that the maximum value of thestress is developed near the grating and mirror mounting area. Thiswould not only result in permanent deformation of optics bench 42 butalso damage the optical components contained therein.

Therefore, a plurality of shock mounts 48 (shock and vibrationisolators) should be used at mounting points of the optics bench 42 andalso at the base of a detector frame 46 to protect the delicate opticalcomponents in case of an impact. The shock mounts also act as vibrationisolators for the optics bench assembly 40. The shock mounts 48 aremodelled as a cylinder made of neoprene measuring 25 mm in diameter and20 mm in length. The results of the drop test analysis with elastomericshock mounts (also referred to as shock absorbers) carried out fordifferent wall thickness starting from 4 mm to 8 mm are shown in FIG.37. The results indicate significant reduction in the stress values.FIG. 37A shows that optics bench 42 with 4 mm wall thickness has maximumstress value of 6.864 MPa. This is lower than the yield strength ofaluminum A 356 (170 MPa). Optical glass can withstand tensile stressesof 6.9 MPa (1,000 psi) and compressive stresses of 345 MPa (50,000 psi)before problems or failure occur, thus an objective is to keep thestress levels lower than 6.9 MPa. Schwertz, K., Useful Estimations andRules of Thumb for Optomechanics, The University of Arizona, 2010.Further reduction in maximum stress values can be achieved by choosingthe optimal wall thickness of the optics bench 42.

The plot of maximum stress developed in the optics bench casing 44during impact versus the wall 75 thickness is shown in FIG. 38. The plotindicates that the maximum stress value in a drop test reaches a minimumfor a wall thickness of 7 mm. The increase in wall thickness increasesthe overall weight of the optics bench assembly 40 which in turnincreases the material cost. Therefore a thickness value between 6 and 7mm will be a good tradeoff between minimizing the stress values andkeeping the weight of the part within acceptable limits. For a thicknessvalue in this range, the maximum stress during impact in the opticsbench assembly 40 with shock mounts 48 will around 5 MPa. This value islower than the failure strength of the glass (6.9 MPa).

Vibration Analysis

Uncontrollable sources of vibration such as fans, air conditioners,pumps, motors, road and rail transportation, etc., can lead to vibrationinduced performance degradation in precision optical components. SinceUV light has wavelength of around 0.2 microns, vibrations with amplitudeeven in sub-micron range can seriously hamper the performance of thedetector by eclipsing valuable data under vibration induced noise.Therefore it is necessary to isolate the critically aligned opticalcomponents from the above sources of vibration disturbances.

Resonance in opto-mechanical devices can be avoided by designing partswith high stiffness so that their natural frequencies of vibration aresignificantly higher than those of anticipated driving forces. Frequencyanalysis was carried out in 3D CAD software program to find the optimalwall thickness that maximizes the natural frequency and stiffness of theoptics bench. In this analysis the mounting points of the optics benchwere fixed and the bench assembly was made to vibrate in differentnatural frequency modes. The first five vibration modes of the opticsbench assembly 40 are shown in FIG. 39. Out of these first fivevibration modes, mode 3 is of major concern because the opticalcomponents vibrate in and out relative to each other. This mode willaffect the performance of the detector because it changes the relativedistances between the optical components which results in loss ofresolution and sensitivity.

The results of the vibration analysis show the natural frequency ofvibration of the optics bench assembly 40 in different modes are eachabove 1400 Hz. This frequency range is much higher than the ambientvibration disturbances, which is typically in the range of 4-100 Hzrange. Such large frequency differences between resonant and excitationfrequencies prevent energy coupling between the optics bench assembly 40and its support structure. Thus the optics bench assembly 40 can beisolated from ambient vibration disturbances. The variation of mode 3(critical mode) natural frequency of optics bench assembly 40 fordifferent wall thickness of optics bench casing is shown in FIG. 40. Thecomponents with high natural frequency of vibration have higherstiffness and are less sensitive to external vibration disturbances.Therefore the optics bench assembly 40 with optimal wall thickness willmaximize the natural frequency of vibration.

The results of the frequency analysis show that increasing the wallthickness increases the natural frequency of vibration. The drop testanalysis shows that a wall thickness of 8 mm increases the stress valuesduring impact/shock loading and also increases the weight as well as thematerial cost. A wall thickness between 6 and 7 mm is a good compromisewhich leads to low stress during drop test, high natural frequency ofvibration (around 1800 Hz), and results in the weight of the opticsbench assembly 40 which is within acceptable limits. Based on theresults of drop test and vibration analysis a wall thickness of 6.35 mm(¼ inch thick) is selected for the optics bench. In terms ofmanufacturability, optics bench with 6.35 mm wall thickness can also beeasily manufactured with conventional or advanced casting methods.

Vibration Isolation

The optics bench assembly 40 can have a natural resonant frequency ashigh as possible and damped. Damping is achieved by selecting anappropriate vibration isolator. Vibration dampers cause the oscillationin a solid body to decay to zero amplitude by diverting the energy fromvibration to other sinks. Damping helps to minimize the duration andamplitude of external vibrations. The first step in selecting avibration isolator is determining the severity of environment in whichthe optics bench assembly 40 is going to be used and the severity of theapplication. These two factors will determine the level of isolationrequired for the optics bench assembly 40.

Liquid chromatography instruments are usually operated in labenvironments so the external vibration disturbances are typically in therange of 4-100 Hz. The major sources of vibration for the optics benchwill be cooling fans in the detector module, motors driving needle drivemechanism, and pumps and motors in sample manager. Considering the ratedspeed of fans and motors which is in the range of 1500-3000 rpm, theexcitation frequencies will be in the range of 25-100 Hz. Therefore, allfrequencies above 25 Hz can be isolated by using vibration isolators.Any excitation frequency below 25 Hz range will not have any significanteffect in the performance of the detector system.

While calculating the correct specifications of the vibration isolators,the lowest disturbing frequency is considered. This is because if thelowest frequency is isolated, then all other higher frequencies willalso be isolated. The theory behind vibration isolation is discussedherein. The calculations for finding the right vibration isolator forthe optics bench system are discussed below. The Mass W of the opticsbench assembly 40 as obtained from a 3D CAD model is 3.086 kg. Assumingcenter of gravity of the optics bench assembly 40 is centrally locatedin the horizontal plane, load W_(L) per mounting point is given byEquation 38.

$\begin{matrix}{W_{L} = \frac{W}{4}} & (38)\end{matrix}$

As discussed herein, for effective isolation of the optics bench fromvibrations disturbances, the maximum isolator natural frequency f_(n) isgiven by Equation 39, where f_(d) is the minimum disturbing frequency.

$\begin{matrix}{f_{n} = \frac{f_{d}}{\sqrt{2}}} & (39)\end{matrix}$The static deflection Δ_(s) for this natural frequency is given byEquation 41, where g is the acceleration due to gravity.

$\begin{matrix}{f_{n} = {\frac{1}{2\;\pi}\sqrt{\frac{g}{\Delta_{s}}}}} & (40) \\{\Delta_{s} = \frac{g}{\left( {2\;\pi\; f_{n}} \right)^{2}}} & (41)\end{matrix}$The required spring rate K for the isolator at the mounting point isgiven by Equation 42.

$\begin{matrix}{K = \frac{{Load}\text{/}{{mount}(W)}}{{Deflection}\mspace{14mu}\Delta_{s}}} & (42)\end{matrix}$

Table 13 shows the calculated values, f_(d), f_(n), Δ_(s) and K for thevibration isolator that would provide the desired level of isolation.

TABLE 13 Selection of Vibration Isolator Maximum External Isolator Loadper Disturbance Natural Static mounting point Frequency f_(d) Frequencyf_(n) Deflection Isolator spring W_(L) (kg) (Hz) (Hz) Δ_(s) (mm) rate K(kg/mm) 0.772 25 17.677 0.8 0.965

Isolators that have f_(n) lower than 17.677 Hz will isolate the opticsbench assembly 40 from external vibration disturbances. Many vibrationisolators matching the specifications shown in Table 13 are availableonline. Bubble mounts from Tech Products as shown in FIG. 41, have anatural frequency of 8 Hz. It is made of neoprene which is chemicallyresistant to most solvents and each mount can take up to 2 kg of load.Also the dimensions of the isolator are compatible with the dimensionsof the optics bench mounting foot.

Transmissibility T of the selected isolators is given by Equation 43.

$\begin{matrix}{f_{n} = {\frac{1}{1 - \left( \frac{f_{d}}{f_{n}} \right)^{2}}}} & (43)\end{matrix}$Table 14 shows that the selected vibration isolators will provide 88.59%isolation to the optics bench.

TABLE 14 Transmissibility of Vibration Isolator Natural frequency ofvibration isolator (Hz) Transmissibility Isolation (%) 8 0.11408 88.59

Thermal Analysis Calculation of Natural Convection Heat TransferCoefficient

Before conducting thermal analysis, the natural convection heat transfercoefficient can be approximated. For calculation simplification theoptics bench 42 is assumed to be a box 77 of dimensions 239×112×261 mmas shown in FIG. 42. The theory behind natural heat transfer coefficientcalculations is discussed by Çengel. Cengel, Y. A., Heat and MassTransfer: A Practical Approach, 3^(rd) ed., McGraw-Hill, 2007.

The ambient room temperature is assumed to be 27° C. (300K). The maximumoperational temperature of the micro-mirror array in DMD which acts asthe major heat source in the optics bench assembly 40 is around 60° C.Texas Instruments, DLP4710 0.47 1080p DMD 1, no. 1, 2015. Thus themaximum temperature difference between the optics bench components andambient air is ΔT=33° C. All side faces of the box can be assumed to be112 mm high vertical surfaces. The natural convection heat transfercoefficient h₁ for vertical faces is given by Equation 44, where ΔT isthe temperature difference and L₁ is the characteristic length.

$\begin{matrix}{h_{1} = {1.42 \times \left( \frac{\Delta\; T}{L_{1}} \right)^{0.25}}} & (44)\end{matrix}$

Table 15 shows the natural heat transfer coefficient for side faces ofthe optics bench, which has characteristic length of 0.112 m.

TABLE 15 Natural Heat Transfer Coefficient for Vertical Surfaces ofOptics Bench Natural heat transfer Characteristic Temperature DifferenceΔT coefficient for vertical Length L₁ (m) (° C.) surfaces h₁ (W/m²° C.)0.112 33 5.88Similarly the top and bottom surfaces can be assumed as rectangularhorizontal surfaces. The characteristic length L2 of the horizontalsurfaces is given by Equation 45.

$\begin{matrix}{L_{2} = \frac{4\; A}{P}} & (45)\end{matrix}$Table 16 shows the characteristic length for top and bottom surfaces,which has an area of 0.0623 m2 and perimeter of 1 m.

TABLE 16 Characteristic Length of Top/Bottom Surfaces of Optics BenchArea of top/bottom surface A Perimeter of top/bottom Characteristic (m²)surface P (m) Length L₂ (m) 0.0623 1 0.249

The natural convection heat transfer coefficient for bottom and topfaces are given by Equation 46, where ΔT is the temperature differenceand L2 is the characteristic length.

$\begin{matrix}{h_{2} = {1.32 \times \left( \frac{\Delta\; T}{L_{2}} \right)^{0.25}}} & (46)\end{matrix}$Table 17 shows the natural heat transfer coefficient for bottom and topfaces of the optics bench 42, which has characteristic length of 0.249m.

TABLE 17 Natural Heat Transfer Coefficient for Horizontal Surfaces ofThe Optics Bench Assembly Natural heat transfer CharacteristicTemperature difference Δ coefficient for horizontal Length L (m) (° C.)surfaces h₂ (w/m²° C.) 0.249 33 4.48The above values of the coefficient of natural convention can be used ina thermal analysis.

Thermal Heat Sources in the Optics Bench Assembly

The proposed UV-LED detector has a maximum of 11 LEDs and each UV-LEDhas a rated power of 1 mW. As described herein, the light from each LEDis transmitted to the light slit at the optics bench 42 through opticalfibers. The amount of heat energy dissipated from the individual opticalcomponents can be calculated from those efficiency values. DMD is themost significant heat source in the optics bench assembly 40. Themaximum heat power output from the DMD arrays is 1.1 W. TexasInstruments, DLP4710 0.47 1080p DMD 1, no. 1, 2015. Certain heat sourcesin optics bench are depicted in FIG. 43.

Steady State Thermal Analysis

The result of the steady state thermal analysis is shown in FIG. 44. Theresult indicates that the maximum temperature gradient in the bench doesnot exceed 0.388K. Since aluminum A356 has coefficient of thermalexpansion of 21.4×10−6 m/mK and the maximum linear dimension of theoptics bench is around 261 mm, a temperature difference of less than orequal to 0.388K will lead to differential expansion of less than orequal to 2.167×10⁻⁶ m.

The above results also show that the steady state temperature of theoptics bench is close to the ambient air temperature (300K in thiscase). Further analysis by changing the ambient air temperature showsthat the variation in the ambient temperature will lead to variation inthe steady state temperature of the optics bench assembly 40. Thereforefor the effective functioning of the detector system, it is necessary todecouple the effects of atmospheric temperature variation and maintainthe temperature of the optics bench at a constant value. This can beachieved by a well-designed thermal management system.

EXAMPLE VIII Thermal Management Considerations

Optical components are extremely sensitive to thermal distortion. Sincethe precision required in optics bench is comparable to wavelength of UVlight, even slight thermal distortion can seriously affect the properfunctioning of the detector light engine. Thus a thermal managementsystem and robust design strategies are critical in maintaining thedimensional stability of the optics bench and isolating it from ambienttemperature variations. The strategies for thermal management in opticsbench are: (1) material selection to reduce thermal distortion; (2)assembly design considerations for thermal management; and (3) Detectorthermal management system.

Thermal Management Considerations During Material Selection

As discussed herein, for good dimensional stability and minimizedistortion due to thermal gradient, a material with low coefficient ofthermal expansion and high coefficient of thermal conductivity isselected. Aluminum A356 has a high value of coefficient of thermalconductivity λ (151 W/mK) and not a high coefficient of thermalexpansion α (21.6×10⁻⁶/K) which results in high

$\frac{\lambda}{\alpha}$ratio as compared to other metals and polymers. This makes aluminum apreferred and commonly used material for optical enclosures.

Assembly Design Considerations for Thermal Management

The optics bench assembly 40 is designed such that all the individualcomponents have their heat sources (DMD arrays, heat sinks, electroniccircuitry and light source) outside the optics bench casing. This allowsthe external thermal management system to rapidly cool the components.The components such as mirrors, gratings and DMD also heat up due toimpinging UV radiation, therefore they are thermally connected to thebody of optics bench which in turn offer a larger surface area to becooled by fans.

Detector Thermal Management System

A thermal management of the detector comprises a system of strategicallyplaced fans, heat sinks and air outlets that provides turbulent air flowinside the optics bench assembly 40 for convection cooling. Thelocations of fans and air outlets are shown in the FIG. 45. The resultof the thermal analysis shows that the thermal gradient in the opticsbench is insignificant. The major concern is temperature variation dueto variation in the ambient temperature. Therefore, the thermalmanagement system can decouple the effects of atmospheric temperaturevariation and maintain the temperature of the optics bench at a constantvalue.

The detector module can be divided into two separate chambers; one forthe optics bench assembly 40 and other for power electronics and controlcircuitry. There is no direct inlet of fresh air in the optics benchchamber. This allows isolating the optics bench assembly 40 fromvariations in the environment. Fresh air is first preconditioned to theright temperature in the power supply and electronic circuitry chamberand then an internal fan circulates the air inside the optics benchchamber. This maintains the temperature of the chamber at a constantvalue. For better temperature control, a silicone strip heater can beadded to the base of the optics bench. The controlled heating by stripheater and cooling by fan, will maintain the temperature of the opticsbench within an optimal operating temperature range.

EXAMPLE IX Manufacturing Process Selection and Considerations

After the optimal wall thickness of the optics bench assembly 40 isdetermined by engineering analysis, appropriate manufacturing processcan be determined according to the selected material, complexity ofdesign, tolerance requirements and cost.

In this embodiment, the material selected for the optics bench assembly40 is aluminum alloy A356. The geometric shape of the optics benchassembly 40 is decided by the optical layout of the detector system. Theoptics bench casing and cover is shown in FIG. 46. The optics benchcasing is an irregular box shape structure with a plate as top cover.The weight of the optics bench casing with top cover as given by the CADsoftware is around 2.4 kg. The basic function of the optics benchassembly 40 is to precisely mount and locate optical components. Thedimensional accuracy required is comparable to wavelength of light.Therefore manufacturing tolerance required in the mounting holes andlocating pins are in order of ±0.01 mm. The annual manufacturing volumeof the optics bench is expected to be around 1000 units. The designrequirements and constraints for optics bench assembly 40 manufacturingare shown in Table 18.

TABLE 18 Design Requirements and Constraints for Optics BenchManufacturing FUNCTION Optics Bench CONSTANTS Material: Aluminum A356Shape: 3D Solid, dish shaped, flat plate top cover Mass: 2.4 kg Sectionthickness: 6.35 mm Minimum tolerance requirement: ±0.01 Annualproduction volume: 1000 OBJECTIVE Minimize manufacturing cost FREEVARIABLES Choice of manufacturing process/processes

As shown by FIG. 47, aluminum can be shaped, joined and finished by awide variety of processes but for polymer manufacturing processes suchas thermoforming, injection molding, blow molding and the like.

The optics bench casing 44 has a shape of an irregular box with a flattop cover. As shown by FIG. 48, the bottom casing of the optics benchassembly 40 which is form of a 3D hollow solid can be manufactured bysand, die, investment or low pressure casting process. The top flatoptics bench assembly cover 70 which is in form of a plate can bemanufactured by sheet forming, electro machining or conventionalmachining process. Advanced manufacturing processes such as water jet,abrasive jet or laser cutting can also be used to cut the top coverprofile from aluminum plates.

The weight of the bottom casing of the optics bench assembly 40 isaround 1.8 kg and the weight of the top cover is 0.5 kg. Given theweight, FIG. 49 shows most of the metal shaping process can be used forthe bottom casing and for the top cover. Adhesives, metal welding andfasteners are suitable joining processes.

The optics bench casing 44 and top cover 70 has a maximum sectionthickness of 6.35 mm. In FIG. 50, the vertical black line shows all thefeasible processes. The sand casting process is not feasible for thislevel of thickness since surface tension and heat flow limit the minimumsection thickness. When only considering the section thickness, allother metal shaping process can be feasible for both bottom casing andthe top cover of the optics bench.

Achieving precise tolerance level of ±0.01 mm is one of the keyconstraint in selection of manufacturing process of optics benchassembly 40. As shown in FIG. 51, none of the metal shaping processesare capable of achieving the required tolerance level. Such tolerancescan be achieved by finishing processes such as precision machining,lapping, grinding and polishing. Therefore the manufacturing of theoptics bench assembly 40 has to be a two-step process. In the first stepa near net shape is achieved by metal shaping process such as casting orextrusion followed by precision machining of features such as surfaces,holes, slots and pins, which has tight tolerance requirements.

One of the most important considerations and the final decidingcriterion for manufacturing process selection is the cost. Usually,manufacturing cost depends on a number of variables such as tooling,overhead and equipment costs. The effect of all these variables can becaptured by a single attribute called economic batch size. Ashby, M. F.,Materials Selection in Mechanical Design Third Edition, 3^(rd) ed.,2005. It helps in deciding which is the most cost effectivemanufacturing process based on the number of units of the part that isto be produced annually. The annual lot size of the optics benchassembly 40 is expected to be around a 1000 units. As shown in FIG. 52,for an economic batch size of 1000 units the manufacturing processesfeasible for aluminum are sand casting, investment casting, lost foamcasting, low pressure casting, forging and conventional machiningprocess. Die casting and powder methods are not feasible manufacturingprocesses for a lot size of 1000 units.

Based on the analysis from the previous sections, it can be concludedthat the best manufacturing process for the bottom casing of the opticsbench assembly 40 is casting followed by precision machining. The topcover can be manufactured from stock aluminum sheets by water-jetmachining process. Since the high precision and tolerance requirementsin the bottom casing of optics bench assembly 40 can be only met byprecision machining process, the choice of casting process is dictatedby cost and complexity of the part. Since the optics bench geometry isfairly complex, the best suited casting process is lost foam orinvestment casting process. A high level of dimensional accuracy, goodsurface finish and near net shapes can be achieved by these processes.

EXAMPLE X Manufacturing Design of Optics Bench Assembly

While designing the optics bench assembly 40, guidelines for lost foamcasting are considered. As shown in FIG. 53, in the optics bench casingdesign, sharp corners are eliminated by fillet radius and there are nosharp angles. Whenever possible, the wall thickness is kept uniform at6.35 mm and sharp transitions in the cross-sectional area are avoided

Selection of Surface Coating

Despite having some good mechanical properties such as good thermalconductivity, good electrical conductivity, good machinabilitycharacteristics; aluminum also has some drawbacks such as it issusceptible to oxidization, abrasion and it is relatively soft whencompared to other metals. Therefore parts made of aluminum need to besurface coated to mitigate or eliminate the drawbacks, avoid degradationof performance, prevent any deterioration in appearance and increase theservice life of the part. In addition to these functional requirements,the coating for the optics bench should absorb any stray light andprevent it from ricocheting off surfaces. Only black colored coatingsappear suitable for this application because black objects are goodabsorber of radiation and blacker the material the more heat it radiatesaway. Dunbar, Brian, NASA-NASA Develops Super-Black Material ThatAbsorbs Light Across Multiple Wavelength Bands.

Considerations for selecting an optical coating include the type ofsubstrate material, spectral requirements, performance requirements,effects elsewhere in the system, manufacturability, environmentaldegradation, maintenance and cost. The surface coatings for the opticsbench are preferably corrosion resistant, wear resistant, resistant tosolvents and chemicals, have high absorption, and low reflectance of awide range of light from UV to IR resistant to UV degradation. Suitablesurface coatings preferably have high thermal stability in wideoperating temperature range, high thermal conductivity, and excellentadhesion to aluminum substrate. Areas of electrical contact or that actas a reference surface for mating surfaces for high precisionapplications may be masked during the coating operation. Methods forsurface coating aluminum include anodizing/plating/chemical films,painting, and vapor disposition. Traditional black paints are notsuitable for optical applications. Black paints can absorb only 90% ofthe incident light. Anodizing is a popular surface coating method.Various anodized coating/hardcoat systems are used for UV, visible andIR light attenuation applications which are also compatible withaluminum over a wide spectral range. These coatings have microprotuberances and cavities that give rise to multiple reflections andscattering of radiation from surface irregularities. Yoder, P.,Opto-Mechanical Systems Design, Fourth Edition, Volume 1: Design andAnalysis of Opto-Mechanical Assemblies, Volume 1, vol. 1, CRC Press,2015. Coatings suitable for the optics bench assembly 40 include lowreflectance of light from low UV to high IR range; thin coatings, so itcan conform to the sharp edges and enhances compliance with precise parttolerance including a wide range of thermal and vibration stability,highly resistant to UV degradation due to its inorganic nature

Protection Against Dust, Airborne Contaminants and Humidity

Moisture and humidity have a damaging effect on the integrity andperformance of optical equipment by condensing on optical surfaces or bycorroding optical components. Other detrimental effects of water as aliquid or vapor inside optics bench assembly 40 include; acceleration ofstress-related fracture propagation and obstruction of transmitted orreflected radiation due to absorption or scatter. High salt content inthe moisture, especially in coastal areas, can accelerate the corrosionand failure of coating on optical and structural components.

Common sources of contamination of optical surfaces are fingerprints,oil from skin, smoke and dust. The contaminants reduce performance byreducing light transmission and intensity by scattering, reflection andabsorption. Another typical contaminant usually found in tropicalcountries with warm climate and high humidity, is growth of localizeddeposits and films of fungus or molds. The microscopic spores of thesemicroorganisms are ubiquitous and can germinate and grow on eventhoroughly cleaned glass surfaces. These organic contaminants degradeoptical performance by introducing scatter or can permanently damageoptical surfaces by etching patterns into the material. Yoder, P.,Opto-Mechanical Systems Design, Fourth Edition, Volume 1: Design andAnalysis of Opto-Mechanical Assemblies, Volume 1, vol. 1, CRC Press,2015.

There are many features in the optics bench assembly 40 design which canisolate the optical components from dust, humidity and airbornecontaminants. The isolation and protection is at two levels, thedetector module level and the optics bench assembly 40 level. First, thedetector has filters of appropriate size at the fresh air inlet ports.The filters prevents large to medium size contaminants and dustparticles from entering into the detector enclosure. Second, the thermalmanagement system is designed so the detector chamber is pressurized byblowing air into the chamber keeping dust out of the system. Third, tocounter humidity and moisture the optics bench chamber is sealedwatertight by using elastomeric gaskets between the optics bench casing44 and the cover 70. As shown in FIG. 54, the gasket 80 is shaped to theprofile of the opening of optics bench. The gasket material can have ahigh chemical and UV resistance. Fluoroelastomer gaskets have highchemical inertness and outstanding UV resistance, and are suited for theabove application. Fourth, dry gas purging is frequently used to createlow dew points within sensitive equipment. The newly built optics benchassembly 40 can be purged of internal gaseous and fluid contaminants byusing dry gas such as nitrogen or helium. The optics bench chamber canbe then evacuated and backfilled with same fresh dry gas.

During periodic maintenance or servicing, the optics bench chamber 41should be evacuated and re-pressurized with dry gas. As shown in FIG.55, the optics bench casing 44 has a dry gas purge filler valve 82 whichis used to purge or pressurize the optics bench chamber 41. Repeated andunnecessary cleaning of the optics bench is not recommended as cleaningunavoidably degrades the thin film coatings on optical instruments. Whencleaned, only approved procedures, materials and solvents compatiblewith optical instruments can be used.

The performance of the optics bench assembly 40 is improved in atemperature controlled and stable environment. Therefore, the end usersshould be encouraged to operate the optics bench assembly 40 in labenvironment with temperature and humidity controlled by HVAC systems forbetter performance and consistent results.

Error Budgeting

Error budgeting is the practice of assigning permissible error tovarious sources on the basis of functionality, feasibility and cost. Itis useful for predicting the accuracy and repeatability of thecomponents and optics bench assembly 40 to determine the appropriatetolerances that can be specified on the optics bench assembly 40 toprovide adequate performance. In the optics bench assembly 40, thesingle most important measure of performance is the resolution. Themajor sources of error in the optics bench assembly 40 which affect theresolution are variations in: (1) the entrance slit width (Δw_(slit));(2) the entrance slit 12 and the grating 14 (ΔL_(α)); the distancebetween the DMD 8 and the grating (ΔL_(H)) and the angular alignmentbetween the DMD and the spectral plane of the grating (Δθ_(DMD)). Theoptical layout depicting the distances L_(α) and L_(H), and theorientation of DMD 8 with respect to the spectral plane of grating, isshown in FIG. 56.

The variation in entrance slit width is wholly the result ofmanufacturing variability. Variation in distance between the entranceslit 12 and grating 14 and between the DMD 8 and grating 14 could becaused by manufacturing variability, thermal expansion and vibrationdisturbances. The vibration induced error is minimized by the use ofvibration isolators as described herein, and is insignificant comparedto the errors due to manufacturing variability and thermal expansion.Therefore it is not considered in the error budget. The angularmisalignment of the DMD can mainly be attributed to the manufacturingvariability.

Equations 47-50 give expressions for each of these variations in termsof the physical sources of the error. The maximum variation in theentrance slit width Δw_(slit) and its relation with the bilateralmanufacturing tolerance t_(slit) is given by Equation 47.Δw_(slit)=t_(slit)  (47)The maximum variation in the angular alignment between the DMD and thespectral plane of the grating Δθ_(DMD) and its relation with thebilateral angular manufacturing tolerance t_(θDMD) is given by Equation48.Δθ_(DMD)=t_(θDMD)  (48)The maximum variation in the distance between the slit and the gratingΔL_(α), and its relation with the bilateral manufacturing tolerancet_(α) and thermal expansion is given by Equation 49, where α_(Al) iscoefficient of thermal expansion of aluminum A356 and ΔT is the maximumallowable change in the temperature of the optics bench.ΔL _(α=t) _(α) +L _(α)α_(Al) ΔT  (49)The maximum variation in the distance between the DMD and the gratingΔL_(H), and its relation with the bilateral manufacturing tolerancet_(H) and thermal expansion is given by Equation 50.ΔL _(H=t) _(H) +L _(H)α_(Al) ΔT  (50)The resolution sensitivity as described herein is given by Equation 51,where NA is the numerical aperture, d_(l) is the linear dispersion ofthe grating and L_(DMD) is the length of the DMD array.

$\begin{matrix}{\frac{\partial R}{{\partial L_{\alpha}}{\partial L_{H}}{\partial\theta_{DMD}}{\partial w_{slit}}} = {{2\;{NA}\;{d_{1}\left( {{\partial L_{\alpha}} + {\partial L_{H}}} \right)}} + {{\partial w_{slit}}{\partial_{1}{+ {\partial{\theta_{DMD}\left( {L_{DMD}{NA}\; d_{1}} \right)}}}}}}} & (51)\end{matrix}$

Substituting expressions for the variations given in Equations 47-50into Equation 51, we get the resolution sensitivity to manufacturingtolerances and variations in temperature, as shown in the Equation 52.

$\begin{matrix}{\frac{\partial R}{t_{\alpha}t_{H}t_{\theta\;{DMD}}t_{sw}} = {{2\;{NA}\;{d_{1}\left( {t_{H} + t_{\alpha} + {\alpha_{A\; 1}{\partial{T\left( {L_{H} + L_{\alpha}} \right)}}}} \right)}} + {t_{slit}d_{1}} + {t\;{\theta_{DMD}\left( {L_{DMD}{NA}\; d_{1}} \right)}}}} & (52)\end{matrix}$The values of NA, dl, LDMD, LH and Lα are determined by the opticaldesign of the detector as shown in Table 19.

TABLE 19 Numerical Values of NA, d_(l), L_(DMD), L_(H) and L_(α) NAd_(l) (nm/mm) L_(H) (mm) L_(α) (mm) L_(DMD) (mm) 0.21 24.3 131.45 137.15The resolution of the optical system is the sum of the inherentresolution R_(o), given by the micromirror pitch of the DMD, and theincrease in resolution ∂R due to error, as shown in Equation 53.R=R _(o +∂) R  (53)

For optical design, inherent resolution is 0.135 nm. The objective oferror budgeting is to find the optimal range of tolerances which willkeep the error within specified limits. The target resolution of theoptical system is 1 nm. Therefore, as Equation 53 shows, ∂R can be lessthan or equal to 0.865 nm, which is the maximum permissible increase inresolution due to errors. The sensitivity of resolution with respect tomanufacturing tolerances and change in temperature is derived fromEquation 52 and depicted in FIG. 57. The error sources to which theresolution is not as sensitive are assigned looser tolerances to allowmore flexibility in manufacturing and to reduce cost. The error sourceswhich drastically effect the resolution even with small changes areassigned tighter tolerance values so that the functionality of thedetector is not effected.

As shown in FIG. 57, the resolution is most sensitive to tH and tα. Bothhave similar effect on the resolution and thus overlap in FIG. 57.Therefore, the tolerance assigned to these factors can be tight, as alarge variability will severely affect the resolution. After t_(H) andt_(α), the resolution is most sensitive is the temperature change ΔT. Asa result, a thermal management system will be required to keep thetemperature within the prescribed window. The resolution is notsensitive to t_(slit) and t_(θDMD), so conventional manufacturingtolerances are sufficient for these factors.

Using Equations 52 and 53, the tolerance values are budgeted keeping inview the target specifications, resolution sensitivity, the design,capabilities of manufacturing processes and expected operatingconditions. Table 20 shows the error budget for the optics bench toachieve the target resolution of 1 nm for the optical system of thedetector.

TABLE 20 Error Budget for the Factors Affecting Resolution R_(o) ΔRT_(H) t_(α) ΔT t_(slit) t_(θ DMD) (nm) (nm) (mm) (mm) (K) (mm) (degree)0.135 0.835 ±0.025 ±0.025 ±3 ±0.002 ±0.25

As shown in Table 20, tolerances t_(H) and t_(α) are in the range ±0.025mm. The angular misalignment of the DMD can be within ±0.25°. Theentrance slit as specified by the optical design has a width of 40microns. For this slit width a tolerance level of ±2 microns isspecified by the manufacturer. The temperature variation can be keptwithin ±3K by a robust thermal management system. A combination ofprecision machining and calibration can be used to achieve the desiredlevel of resolution and minimize the error. The optics bench casing canbe manufactured using the lost foam investment casting process. Thetypical linear tolerances with lost foam investment casting are 0.005mm/mm. The maximum linear dimension of optics bench is around 250 mm, sothe tolerances on the casted bench will be around ±1.25 mm. This is wellabove the desired tolerance of ±0.025 mm.

Therefore, casting can be followed by precision machining. Toaccommodate post-machining steps, sufficient machining allowance can beincorporated in the design of the optics bench casting. The tolerancesachieved by machining with a 5 axis milling machine range from ±0.01 mmto ±0.005 mm. Ashby, M. F., Materials Selection in Mechanical DesignThird Edition, 3rd ed. 2005; Woldman, N. E. and Gibbons, R. C.,Machinability and Machining of Metals, McGraw-Hill, 1951. The tolerancesnear the lower limit are more common and the tighter tolerances can beachieved by high precision, high cost machines. Therefore, postmachining the optics bench with tolerances of ±0.025 mm, can beachieved. However this level of tolerance will come at an increasedcost. If cost is a constraint, tolerances in machining can be relaxed bycompromising on the resolution of the optical system. The order ofoperations for machining can be as follows: (1) the optics benchassembly 40 is clamped with the top opening facing downwards; (2) thefour feet and their mounting holes are machined; (3) the bench is fixedto a rotary table with precision pins through the mounting holes and themounting feet clamped against the table; and (4) the machining ofcritical surfaces and holes can be carried out with this setup on 5-axismill.

After machining, the optics bench can be assembled. The manufacturingtolerances for angular orientation are well within the designspecifications. Using an oversized DMD will allow much of thecalibration to take place automatically. To achieve the requiredtolerances for L_(H)and L_(α), the optical system can be manuallycalibrated. Therefore, calibration effort and time should be focused onthe linear distances L_(H) and L_(α) as shown in FIG. 58.

The calibration mechanism 84 is shown in FIG. 59. A threaded shaft 86will allow the grating 14 to move linearly and adjust the distance L_(H)and L_(α). The angle between the axis of the grating 14 and L_(H) andbetween axis and L_(α), are small. Therefore, linear movement along thegrating axis will result in 89% and 99% movement along L_(H) and L_(α)respectively. After achieving the desired resolution, the grating can belocked down to the accurate location using the clamping mechanism orthreaded fastener 88. The above proposals need to be tested andvalidated by prototyping and extensive testing.

EXAMPLE XI Prophetic Prototype of Optics Bench Assembly

A looks-like physical prototype of the optics bench assembly 40 was 3Dprinted using a Fused Deposition Modeling (FDM) process to check anyissues during assembly and service. The pictures of the prototype areshown in FIG. 60. The optics bench casing, cover and mounting bracketswere all 3D printed. All other off the shelf and custom made opticalcomponents such as the mirror 56, grating 14, photodiodes 62,64, flowcell 66, light entrance slit 12 and beam splitter 60 were mounted on theprinted parts. During assembly of components no major issues wereobserved. There was no clash of assembled components and assemblyprocess was seamless. The slots in the optics bench 42 had sufficientclearance to allow unobstructed assembly path for optical components forentry in the optics bench 42 without scratch or damage. There was alsounobstructed access to the tools used for assembly. But utmost careneeds to be taken during the assembly process and it can be carried outin a clean room with dry environment to prevent contamination of opticalcomponents.

The mechanical design of the optic bench assembly is based on theoptical layout of the UV-LED based Liquid Chromatography detector. Theoptic bench assembly is broken down into smaller subassembliescontaining optical and structural components. The subassemblies areattached to the optics bench casing using fasteners and aligned andlocated using precision machined locating pins. All the subassembliesare designed to be independently replaceable to facilitateserviceability. The assembly is also designed so the thermal heatsources of the opto-electrical components are kept outside the opticsbench casing.

Aluminum A356 was found to be a suited material for optics benchassembly 40 to minimize vibration sensitivity, thermal distortion anddeformation during impact loading. The material is also resistant to UVdegradation, easily available and is also cost effective. After droptest and vibration analysis, it was found that a uniform wall thicknessof 6.35 mm (0.25 inches) increases the stiffness and natural frequencyof the optics bench far above the disturbing frequencies and minimizesthe stress during drop test. The weight of the assembly falls underacceptable limits.

To isolate the assembly from vibration disturbances and protect theoptical components during shock loading, vibration and shock mounts wereincorporated in the assembly. Thermal analysis showed that the thermalgradient in the optics bench due heat generated by opto-electricaldevices and radiation absorption is not significant. But it was foundthat the optics bench temperature is sensitive to variation in theambient temperature and thus a thermal management system is needed todecouple the effects of environmental temperature variation and maintainthe temperature of the optics bench at a constant operating temperature.

Based on the selected material, complexity of design and functionalrequirements, lost foam casting or investment casting followed byprecision machining and water jet cutting of aluminum plate was a suitedmanufacturing process for both the optics bench bottom casing and topcover. Coating the optics bench with Martin black dye anodized coatingor vacuum deposited coating with Acktar optical black™ preventscorrosion and wear, and also to absorb stray UV radiation. Features suchas sealing the bench watertight using fluoroelastomer gaskets and drygas purging to protect the optical components from contaminants, dustand moisture, were also incorporated.

The Diversity of Applications for the Detector

FIG. 61 provides a pie chart of 2013 market demand for HPLC systems. Thechart was generated in part with data acquired from the U.S.Pharmacopeial Convention (“USP”) via the marketing division of a leadingliquid chromatography equipment manufacturer. The USP is a scientificnon-profit organization that sets the standards for the identity,strength, quality and purity of medicine, food ingredients, dietarysupplements and the like to be manufactured, distributed and consumedworldwide.

USP undertakes is to develop and maintain monographs for variousmedications, food ingredients, dietary supplements, etc. A monograph isa standard which details a substance and provides its name; itsdefinition; packaging, storage and labeling requirements; and all theinformation on tests required to ensure that the substance is ofappropriate strength, quality and purity States, et al., USP FACT SHEET,USP Standards: Monographs (Written Standards) What is a Monograph?(2008). Key information in these monographs includes a specificwavelength that is recommended to detect the substance (also referred toherein as a “constituent” or a “compound”).

As shown in FIG. 62, data shows that there are a number of testingmethods that utilize specific wavelengths, e.g. nearly 30% of theregistered LC methods are use a wavelength of 254 nm. A number of suchpreferred wavelengths exist and use of such wavelengths is most oftenestablished in standard tests for various substances. On the other hand,increasingly, companies are more interested in the response of new andunknown substances to the whole spectrum of light (UV-visible) andrequire more flexibility in wavelength selection. Current UV absorptiondetectors are generally designed for the wavelength range of 180 nm to350 nm and many substances are known to absorb light in this rangeScott, R. P. W., Liquid Chromatography Detectors, Journal ofChromatography Library, 1^(st) ed., vol. 11, Elsevier, 1986. On thebasis of this gathered information and data, we identified threecustomer segments for the detector described herein as shown in Table21.

TABLE 21 Proposed Customer Segmentation for the Detector S. No. CustomerSegment Requirement 1 Single Wavelength Requirement 2 Wavelength varyingcapability requirement in the UV range 3 Wavelength varying capabilityrequirement in the UV-Visible range

Proposed Configurations for the Detector

Considering the customer segments, three configurations for the detectorand estimated market share are provided in Table 22 below.

TABLE 22 Identified Configurations for the Detector Estimated S. No.Configuration Market Share 1 Single wavelength configuration, withability 50% to change wavelengths if needed 2 UV range scanningcapability 40% 3 UV-visible range light scanning ability 10%

For estimating the market share, we theorize that 90% of the QC/QA andthe analytical service segment will be interested in the singlewavelength configuration. Of the remaining customers, we surmise that80% will have their demand met by the UV range scanning capabilitydetectors and the rest will want the UV-visible range scanningcapability. The estimated market share gives some indication of thepossible sales scenario for the detectors.

Existing UV Light Detectors

A fixed wavelength detector is relatively simple in design andconstruction, and the schematic for the light path in such a detectorprovided in FIG. 63. For the scanning detector, a basic schematicdepicting its working is shown in FIG. 64. In this type of detector, theprism/dispersion grating is moved via a motorized mechanism for thepurpose of selecting different wavelengths. However because of theinertia of the prism/grating and motorized mechanism, it is not toswitch between wavelengths at high speeds.

For the photodiode array detector, the basic schematic is shown in FIG.65. This detector appears to be the more costly of UV absorptiondetectors available in the market, with the key cost coming from thephotodiode array.

Current Light Sources Used in UV Detectors

As described herein, light sources for use with UV-Visible Lightdetectors for liquid chromatography have evolved over time. The earliestsources were metal-vapor discharge lamps, which produced a discretespectrum. Common is the mercury-vapor lamp, which produces a peakwavelength at 253 nm and considered a legacy wavelength as it serves asthe basis for a number of current chromatographic methods. Because theselamps had a discrete spectrum, they were favored in the construction ofthe fixed wavelength detectors. These are now superseded by gasdischarge lamps and incandescent lamps, both of which produce acontinuous spectrum and are used in scanning and photodiode array typedetectors.

UV LEDs and Implications for Detector Architecture

The detector 4 described herein can use high powered UV LEDs as a lightsource 50. High power LEDs (in the milliwatt and higher range) emittinglight in the near-ultraviolet range (300 to 400 nm) are currentlyavailable. They are manufactured by depositing Gallium-Nitride orAluminum-Gallium-Nitride on a sapphire substrate. Deep UV LEDs withAlN-AlGaN based LEDs have already been demonstrated at wavelengths of210 nm to 360 nm Hirayama, H., et al., Development of 230-270 nmAlGaN-Based Deep-UV LEDs, Electron. Commun. Japan, Vol. 93 (2010).However, this type of LED has considerably low efficiencies compared totraditional visible light LEDs. By using metal-organic chemical vapordeposition methods to grow high quality AlN buffers on sapphiresubstrates, LEDs at 261 nm and 227.5 nm with power 1.65 mW and 0.15 mWrespectively were demonstrated. Id.

High power deep UV LED's are a relatively new product. The deep UV LEDsuse AlN as the substrate itself and have an optical output of 0.5 mW or1 mW. Because of the similarity of the material which results in lowerdensity of dislocations, AlGaN UV LEDs grown on low density bulk AlNexhibit distinct improvements in light output and thermal management.Ren, Z., et al., Heteroepitaxy of AlGaN on Bulk AlN Substrates for DeepUltraviolet Light Emitting Diodes, Appl. Phys. Lett., Vol. 91, No. 5,90-92 (2007). Deep UV or UVC LEDs, as shown in FIG. 66, in peakwavelengths from 250 nm to 280 nm are currently available. However,because UV LEDs are a developing technology, these LEDs will play a moreinfluential role in determining product architecture, especiallymodularity.

While looking at the product architecture for the detector, a key aspectin LED usage is their limited range of wavelengths as compared to thedeuterium UV lamp, making this a technological constraint. The halfintensity range for these LEDs is essentially +/−6 nm from the peakwavelength of the LED, so a single LED would cover an band of 12 nms. Asshown in FIG. 67, the approximate spectral distribution of a UV LEDwhose peak wavelength is 260 nm. The UV LEDs are also considerablysmaller than UV lamps. They can be approximated as a cylinder withdiameter 9 mm and height 6 mm. Crystal IS, High Performance WC LEDs forInstrumentation.

The deep UV LED technology is currently at a nascent stage of itslifecycle and is expected to mature for the next few years. From a costperspective, while the current iterations of the LEDs are expensive,they are expected to become cheap as the technology is established andmass production becomes the norm.

These two aspects: (1) the short spectrum range; and (2) the currentstate of the UV LED technology should be considered when designing thearchitecture for the detector 4. These two considerations move towards amodular approach for UV LEDS as a component in the detector 4. UV LEDSmeet the criteria for modularity as described herein.

Optical Fibers for UV LEDs and Implications for Detector Architecture

The use of optical fibers as a light delivery mechanism allows forflexibility in the product architecture. With optical fibers, there isless need to place the light source 50 close to the remaining opticalelements, as the fiber can easily route the light to them from thesource.

For UV light applications down to the wavelengths of 200 nm, opticalfibers made by using silica-glass as the core material andtetrafluoroethylene-hexafluoropropylene copolymer or methylpolysiloxaneas the sheath material are appropriate. Such optical fiber systems areoptically transparent between 200 nm to 2200 nm range with the onlyexception being at an absorption band at 1400 nm. These fibers are alsothermally stable up to temperatures of 250° C. and show no loss oftransmission efficiency. Dislich, H., et al., Light Guide Systems forthe Ultraviolet Region of the Spectrum, Angew. CHEMIE Int. Ed. English,Vol. 12, No. 6, (1973).

Digital Micromirror Device

As described above, the DMD is essentially a light modulator, made up ofan array of micro mirrors, each of which can be moved independently. Thedevice has a memory cell below the mirror array where data is loaded tocontrol the tilt angle of each individual mirror electrostatically. Eachmirror has the two states, either +x degrees or −x degrees where x isusually 12 degrees or 17 degrees. This mirror array in a DMD is coveredby a transparent window for protection as well as to control theincident light properties. The rate at which the orientation of theindividual mirrors can be changed varies from about 4 kHz for the mostbasic variants to 32 kHz for the advanced variants. The first DMD wasmade by Texas Instruments, See e.g., U.S. Pat. No. 5,504,575,incorporated herein by reference. DMDs are a relatively maturetechnology, with Texas Instruments introducing DMD incorporatingcommercial products in 1996. DMDs are used in digital cameras, HDtelevisions, digital projectors. FIG. 68 shows the mirror array of theDMD.

While the currently available DMDs are specified to work in the visiblelight to infrared light region only, research is being done on how toadapt these devices for UV applications. This research is especiallydriven by the use of the DMDs in maskless lithography devices. DMDs withreliable operating characteristics down to 390 nm have already beendemonstrated and Texas Instruments is working to develop DMD's capableof working down to the 200 nm ranges. Thompson, J., et al., DigitalProjection of UV Light for Direct Imaging Applications, DLP Technologyis Enabling the Next Generation of Maskless Lithography, 2008. Researchin this area has also demonstrated viable operation of DMDs withspecialized windows of sapphire or quartz down to 265 nm wavelengthlight. Fong, J. T., et al., Advances in DMD-Based UV ApplicationReliability Below 230 nm, Proc. SPIE, Vol. 7637 (2010). So it isreasonable to expect development of viable DMD's capable of operating inthe deep UV region.

As noted herein, the detector can use a diffraction grating to shine thespectrum of light from a UV LED array on to a DMD, then select therequired bandwidth of light by switching on the required micromirrorrows and using the rest of the micromirror array in the off-position todirect the remaining light elsewhere. Because of the extremely smallsize of the micromirrors compared to a motor mounted diffractiongrating, the detector can switch wavelengths at extremely high speeds.This capability is not present in current detectors.

Functional Schematic

As shown in FIG. 69, after the decomposition process, the 21 identifiedfunctional elements are arranged in a functional schematic to show howthe detector should work. FIG. 69 depicts the different type ofinteractions that can occur in the detector. There is a light source 50to generate light of different wavelengths along with a referencewavelength light source 50. Light from these two sources is collectedand sent through the system by imitating a point source. This isnecessary for achieving good optical resolution as discussed herein.Light is then split into its constituent wavelengths and the requiredwavelengths are selected and focused. This focused light is split into asample beam and a reference beam which is recorded for comparison to thesample beam after it has gone through the liquid chromatography sample.

To run the detector 4, power has to be supplied to it. The incomingpower has to be converted to the required voltages for the differentcomponents to be distributed to them, and then the various components,especially the electrical ones have to be controlled. The lightmeasurements have to be interpreted and this data has to be communicatedto the control software as well as input from the rest of the liquidchromatography system.

EXAMPLE XII Proposed Architecture Scheme for Configuration 1

As described herein, configuration 1 is an embodiment of a singlewavelength type detector which has the capability to switch wavelengthsif required. This is suitable for the QC/QA and analytical customer whouses a single wavelength most of the time, yet would prefer thecapability to change the wave length when needed. The functionalcomponents of the detector 4 are shown in FIG. 70. A schematic of anembodiment of the physical components of the detector 4 is provided inFIG. 71. Having a single LED 6, this architecture represents anefficient method of manipulating the light. In this embodiment of thedetector 4, only a single UV LED is considered, which can have a halfheight wavelength range of about 12 nm. The range can be furthernarrowed to the required wavelength by the using narrow pass opticalfilters which can narrow the half height bandwidth up to 2 nms. The LED6 can have a microchip to identify it to the system. Also, because thisconfiguration works with a single wavelength, there is no need for areference light source 50 as it would be redundant and linked with theLED itself. Then a mirror or a lens can be used to focus the light on abeam splitter, which would split the light into a reference beam for thereference photodiode and a sample beam which would go through the flowcell and be recorded by the sample photodiode. The optical benchassembly 40 can support and hold the optical components in place.Temperature sensors would measure the internal temperature of thedetector 4 and appropriately placed fan(s) would regulate thetemperature inside. Power would be supplied to the detector through apower cord and would be converted to the required voltages using a powersupply unit, which could be an off-the-shelf component or a customizedbuild. For the electronic control, circuitry incorporating amicrocontroller with the requisite analogue to digital converters forthe photodiodes will be used. The circuitry would also communicate withthe rest of the liquid chromatography system and the control software.Finally, a product chassis would enclose the detector 4 to protect itfrom outside conditions. A key innovation is making the LEDs modular soas to allow the customer to change the wavelength if and when required.

EXAMPLE XIII Proposed Architecture Scheme for Configuration 2 and 3

For Configurations 2 and 3, the linking of functional elements tophysical components is shown in FIG. 72 and a schematic derived fromthis set of choices is shown in FIG. 73. Both configurations 1 and 2allow scanning through a range of wavelengths with simultaneouslymeasuring the response of the liquid chromatography sample to variouswavelengths. As discussed herein, current methods employ either aturnable prism/grating or split the light on to a photodiode array afterit has passed through the sample. Use of the digital micro-mirror device(“DMD”) in combination with a diffraction grating to switch wavelengthsat high speeds is proposed. As the range of wavelengths required fordetectors would be more than what is provided by a single UV LED, anarray of such LEDs would be needed. In this array, the LEDs would bemodular and each would have a microchip to identify itself to thesystem.

For Configuration 2, the digital micro-mirror array would cover the UVlight range while for Configuration 3, the digital micro-mirror arraywould cover the UV and visible light range both. To collect and combinethe light from these LEDs, optical fibers would be used. These opticalfibers would end on a slit, which would act as a point source anddetermine the lower limit on the resolution of the system. The lightbeam would then be split into its constituent wavelengths and madeincident across the DMD 8. By controlling the digital micro-mirrorarray, it would be possible to select specific wavelengths as well asthe bandwidth of wavelengths at high speed. The selected light wouldthen be incident on a beam splitter and split into the reference beamand the sample beam. The reference beam would be recorded by thereference photodiode and the sample beam would pass through the flowcell 66 carrying the liquid chromatography sample. The rest of thefunctional elements are linked to similar physical elements as inConfiguration 1. This schematic was mapped out on a design structurematrices (“DSM”) for studying the key interactions to define productarchitecture at system level.

Clustering Through DSM for System Level Architecture

Key interactions in the detector for Configurations 2 and 3 are thelight interaction and the spatial interactions. Configuration 1 was notconsidered for DSM analysis as it is a relatively simple design. Aselectric power and information can be easily transmitted throughflexible wires, these interactions were not considered for system levelgrouping. It should be noted, that these clustering are not final butare a method to look at the effect of the proposed clustering oninteractions between various sub-systems.

Suggested Clustering on the Basis of Light Interactions

The clustered DSM for light interactions in the detector 4 is shown inFIG. 74. The clustering has been done manually minding the variousconsiderations discussed so far and since the UV LEDs have to be keptmodular for technological considerations, they are not included in anycluster. Cluster 1 consists of the optical fibers and the referencelight source, a small mercury lamp generating light at 254 mn. It willlink with the UV LEDs. Cluster 2 consists of all the remaining opticalelements and the optical bench holding the optical elements together.Such a grouping allows for internalization of a number of interactionsand the design teams for each cluster will have to take specialconsideration of only 2 optical interactions—the LED to optical fiberinteractions and the optical fibers to the slit in the optical bench.

Suggested Clustering on the Basis of Spatial Interactions

The spatial interaction for various components in the detector wasmapped out on a DSM and the clustering was done as shown in FIG. 75.These interactions refer to the adjacency between the variouscomponents. The clustered DSM for spatial interactions shows that evenwith the suggested clustering, there are still numerous out-of-chunkinteractions.

Taking into account the market, technology and the key interactions, thefinal architecture for each of the three configurations was developed.

Product Architecture for Configuration 1

The product architecture for Configuration 1 with the selectedcomponents and subsystems is shown in FIG. 76. This grouping was donekeeping in mind the technological considerations and discussions withthe optical and mechanical designers for such detectors as discussedherein.

Led Module

For Configuration 1, the LED module comprises the LED, a narrow passoptical filter to select a single wavelength and a microchip to identifythe wavelength of the LED module to the system. This enables thecustomers to buy the LED module of the wavelength they are interestedin.

Optics Bench Assembly 40

The optics bench assembly 40 comprises the optics bench casing to holdthe remaining optical elements—the mirror/lens, the beam splitter, thereference photodiode & the sample photodiode. The optical casing willalso have interfaces for the LED module and the flow cell module. Thecasing should be designed in such a manner to allow for easy replacementof the optical elements in case of wear.

Flow Cell

Each liquid chromatography system manufacturer has its own variety offlow cells, varying in optical path length and the volume of the sampleexposed to the light. The flow cell can accommodate various flow cellsas well as provide a standard interface for them to the optical bench.

Thermal Management System

The thermal management system will consist of temperature sensors andfan(s) to maintain a steady temperature inside the detector. It willhave to be setup to be able to take into account heat from all sources.

Power Cord

The power cord has been kept as a separate module as its design willvary from country to country.

Power Supply Unit

The power supply unit can be a standard off-the-shelf component or acustom built unit which will convert the wall electrical power input tothe various voltages required by the other components.

Electronic Control System

The electronic control system will comprise of the circuitry includingthe microcontroller, the analogue to digital converters and the variousancillary electronics to control the detector, and to communicate withthe control software and the rest of the liquid chromatography system.

Product Chassis

The product chassis will enclose the entire detector and protect it fromoutside elements and should have an appropriate receptacle for the LEDmodule in conjunction with optics bench.

Product Architecture for Configurations 2 and 3

For Configurations 2 and 3 of the detector 4, the developed productarchitecture is shown in FIG. 77.

Led Module

The LED module for Configuration 2 and 3 comprises the LED and themicrochip identifying the specific LED to the system. The LED modulescan have electrical and information interfaces for taking power andallowing the microchips to be read by the system.

Optical Bus

The optical bus is an LED array holder with receptacles that fit the LEDmodules. The optical bus can also have a small mercury lamp to act as areference source for the system. Optical fibers from the receptacles andthe mercury lamp can take the light to the entrance of the opticalbench. It should be noted here that the receptacles in the optical bushave to be designed such that they can supply power to the LED modulesas well as read the microchips in them to identify which wavelengths arethey emitting. The optical bus can be the common bus chunk and the LEDmodules will have a bus-modular architecture with the optical bus.Configuration 2 can have about 11 LED receptacles to cover the UV rangewhile Configuration 3 can have a greater number of receptacles to extendthis range to the visible spectrum.

Optical Bench

The optical bench for Configurations 2 and 3 can be larger toaccommodate more optical elements. The casing of the optical bench canhold the slit of the required width to determine the resolution of thesystem, the optical fibers from the optical bus will interface with thisslit. It can also hold the remaining optical elements in place asrequired by the optical design, these being the diffraction grating, theDMD, the focusing mirror, the beam splitter, the reference and samplephotodiode. It should be noted that in these two configurations, theoptics bench assembly 40 also has to absorb the light that the DMDshunts away for the unselected wavelengths. Furthermore the optics benchassembly 40 will have the appropriate interface for the flow cellmodule. The casing is designed with the issues of assembly as well asserviceability in mind. It would be beneficial if a slot-modulararchitecture was followed in its design, with each optical elementfitting into its own specific slot and being easily accessible forreplacement.

Flow Cell

Each liquid chromatography system manufacturer has its own variety offlow cells, varying in optical path length and the volume of the sampleexposed to the light. The flow cell chunk should be able to accommodatethese various flow cells as well as provide a standard interface forthem to the optical bench.

Thermal Management System

The thermal management system will consist of temperature sensors andfan(s) to maintain a steady temperature inside the detector 4. It willhave to be setup in such a manner to account for all heat sources. Thissystem will be more critical for Configurations 2 and 3 as the DMD willalso generate heat in these.

Power Cord

The power cord will be a separate module as its design will vary fromcountry to country.

Power Supply Unit

The power supply unit can be a standard off-the-shelf component or acustom built unit which will convert the wall electrical power input tothe various voltages required by the other components.

Electronic Control System

The electronic control system will comprise of the circuitry includingthe microcontroller, the analogue to digital converters and the variousancillary electronics to control the detector 4, and to communicate withthe control software and the rest of the liquid chromatography system.

Product Chassis

The product chassis will enclose the entire detector 4 and protect itfrom outside elements and will expose the optical bus to the customerfor switching out the LED modules.

Implications of the Detector Architecture Product Changes

There are two key elements that are likely to require upgrades in thedetector 4 as their technology matures: the UV LEDs and the DMD. Bymaking the LED chunk completely modular as shown in the architecture, itis possible for the company manufacturing such a detector to offercustomer upgrades as soon as they are available. The DMD on the otherhand is part of the optics bench assembly 40 and while the optical benchassembly should be designed keeping in mind serviceability issues anychange involving the size of the DMD will lead to a redesign of theoptical bench. A key feature in the DMD that is still in thedevelopmental phase is the window covering the micro-mirror array, fortheir use in the UV region. Henceforth it may be possible to upgrade asame size DMD with an improved window in the detector.

Product Variety

As noted above, there are three key customer segments that have beenidentified and a suitable product architecture for three productconfigurations developed. Table 23 shows the differentiation plan forthe three configurations and represents how the three products will bedifferent for the customer and the market in terms of the variouschunks.

TABLE 23 Differentiation Plan for Three Detector ConfigurationsDifferentiating UV Region UV-Visible Region Attributes Single WavelengthScanning Scanning LED Module LED with optical LED with full LED withfull filter: optimized for possible emission possible emission singlewavelength spectrum spectrum Optical Bus Not applicable Smaller opticalbus Larger optical bus to to cover UV range cover the UV-visible rangeProduct Chassis Smaller Chassis Large Chassis Large Chassis

Component Standardization

Table 24 shows the commonality plan for the three detector 4configurations. This plan considers all the chunks and shows howdifferent chunks will be common or different across the threeconfigurations. For each configuration, the type of the chunk that willbe used in it is shown.

TABLE 24 Commonality Plant for Three Detector Configurations UVUV-Visible Single Region Region Chunk Number of types WavelengthScanning Scanning LED Module 2 (with multiple Type 1 Type II Type IIsubtypes depending on wavelength) Optical Bus 2 NA Type I Type IIOptical 3 Type I Type II Type III Bench Flowcell 1 (with subtypes Type IType I Type I depending on the liquid chromatography system) Electronic2 Type I Type II Type II Control System Thermal 1 Type I Type I Type IManagement System Power Chord 1 Type I Type I Type I Power 2 Type I TypeII Type II Supply Unit Product 2 Type I Type II Type II Chassis

After the architectural scheme was finalized, Configuration 2 wasselected for detailed. Even though Configuration 1 has a simplifieddesign and Configurations 2 and 3 have a complex design incorporating adigital micro-mirror device along with the UV LEDs and share similarchunks. Furthermore, it was estimated that this configuration wouldappeal to approximately 40% on the market as discussed herein.

Summary

To summarize, architecture for embodiments of the liquid chromatographydetector using UV LEDs in instead of traditional deuterium lamps wasdeveloped. Three possible product configurations have been identifiedand two architectural schemes were developed and are described in theexamples provided herein.

We claim:
 1. A detector for liquid chromatography comprising: a lightdelivery system comprising a light source that emits light having aplurality of wavelengths; and a wavelength selection module opticallycoupled to the light delivery system, the wavelength selection modulecomprising: a first spectrally dispersive optical element to receive thelight from the light delivery system and to provide diffracted lighthaving a linear dispersion of the wavelengths; a digital micro-mirrordevice configured to receive the diffracted light and to selectivelyreflect two or more of the wavelengths into an output beam; and anoptical output subsystem optically coupled to the digital micro-mirrordevice to receive the output beam from the digital micro-mirror deviceand provide a single image that simultaneously includes the two or morewavelengths in the output beam.
 2. The detector of claim 1 furthercomprising a flow cell disposed along an optical path between the lightdelivery system and the wavelength selection module.
 3. The detector ofclaim 1 further comprising a flow cell disposed to receive the outputbeam of the wavelength selection module.
 4. The detector of claim 1wherein the optical output subsystem comprises at least one focusingelement and a spectrally dispersive optical element.
 5. The detector ofclaim 1 further comprising a focusing element that optically couples thelight delivery system to the wavelength selection module.
 6. Thedetector of claim 1 wherein the linear dispersion of the wavelengths isan angular dispersion of the wavelengths in the diffracted lightprovided by the first spectrally dispersive optical element.
 7. Thedetector of claim 1 wherein the first spectrally dispersive opticalelement comprises a focusing element and a grating.
 8. The detector ofclaim 1 wherein the first spectrally dispersive optical element is aconcave grating.
 9. The detector of claim 1, wherein the output beam ofthe wavelength selection module includes one or more wavelengthsselected to match one or more spectral absorption features of an analyteof interest.
 10. The detector of claim 1, wherein the wavelengthselection module further comprises an optical attenuator.
 11. Thedetector of claim 1, wherein the digital micro-mirror device isconfigurable as a variable slit having a dynamically defined width and aheight.
 12. The detector of claim 1, wherein the digital micro-mirrordevice is a first digital micro-mirror device and wherein the wavelengthselection module further comprises a second digital micro-mirror devicedisposed between the light delivery system and the spectrally dispersiveoptical element, the second digital micro-mirror device having aplurality of micro-mirrors configurable to define a variable entranceslit having a width and a height determined by an orientation of aplurality of the micro-mirrors.
 13. The detector of claim 1, wherein thedigital micro-mirror device is a first digital micro-mirror device andwherein the wavelength selection module further comprises a seconddigital micro-mirror device positioned to receive the output beam fromthe first digital micro-mirror device, the second digital micro-mirrordevice having a plurality of micro-mirrors configurable to define avariable exit slit having a width and a height determined by anorientation of a plurality of the micro-mirrors.
 14. The detector ofclaim 1, wherein the plurality of wavelengths includes a plurality ofultraviolet wavelengths.
 15. The detector of claim 1 further comprisinga light detector disposed at a location of the single image.
 16. Thedetector of claim 15 wherein the second spectrally dispersive opticalelement is a grating.
 17. The detector of claim 1 wherein the opticaloutput subsystem comprises: a first lens to receive the output beam andto provide, for each of the two or more wavelengths in the output beam,a collimated beam; a second spectrally dispersive optical element inoptical communication with the first lens to receive the two or morecollimated beams and generate a diffracted beam wherein each of thecollimated beams is parallel to each of the other collimated beams; anda second lens in optical communication with the second spectrallydispersive optical element to focus each of the collimated beams at acommon focus.